Ethylene-based polymer, polyethylene-based resin composition and use thereof, catalyst component for olefin polymerization, olefin polymerization catalyst containing the component, and method for producing ethylene-based polymer by using the catalyst

ABSTRACT

An object of the present invention is to provide a polyethylene-based resin composition excellent in the moldability and at the same time, excellent in the balance between impact strength and stiffness as well as in the transparency, and a molded product and a film, which are obtained by the molding of the polyethylene-based resin composition. The polyethylene-based resin composition of the present invention comprises from 41 to 99 wt % of (A) an ethylene-based polymer satisfying specific conditions and from 1 to 59 wt/of (B) an ethylene-based polymer satisfying specific conditions, wherein MFR of the composition as a whole is from 0.05 to 50 g/10 min and the density is from 0.910 to 0.960 g/cm 3 .

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a Divisional application of U.S. Ser. No.14/008,965, filed Sep. 30, 2013, now allowed; which is a 371 ofPCT/JP2012/058491, filed Mar. 29, 2012, the disclosure of which isincorporated herein by reference in its entirety. This applicationclaims priority to Japan Patent Application 2011-073937, filed Mar. 30,2011; and Japan Patent Application 2011-073945, filed Mar. 30, 2011, thedisclosures of which are incorporated herein by reference in theirentireties.

TECHNICAL FIELD

The present invention relates to an ethylene-based polymer having adeveloped long-chain branched structure and excellent in themoldability. As another aspect of the present invention, the presentinvention relates to a novel polyethylene-based resin composition anduse thereof. More specifically, the present invention relates to apolyethylene-based resin composition excellent in the moldability andcapable of producing a molded product excellent in the balance betweenimpact strength and stiffness as well as in the transparency, and amolded product and a film each obtained by the injection molding,compression-injection molding, rotational molding, extrusion molding,hollow molding or blow molding of the polyethylene-based resincomposition. Furthermore, the present invention relates to an olefinpolymerization catalyst component containing a specific metallocenecompound, an olefin polymerization catalyst containing the component,and a method for producing an olefin-based polymer by using thecatalyst.

BACKGROUND ART

Recently, a film, a sheet, an injection molded product, a pipe, anejection molded product, a hollow molded product and the like, which aremade of a plastic, are used actively in various industrial fields. Amongothers, a polyethylene-based resin (ethylene-based polymer) findswidespread use, because this is, for example, inexpensive, lightweightand excellent in the moldability, stiffness, impact strength,transparency, chemical resistance and recyclability. In general, moldingof the polyethylene-based resin is preformed in a molten state. However,in the case of an ethylene-based polymer alone, its meltingcharacteristics may be insufficient, for example, in terms offlowability or the elongational viscosity may be inadequate, and in manycases, sufficient moldability can be hardly ensured or solid physicalproperties such as transparency and stiffness may lack.

As for the measure taken to compensate these deficiencies, ahigh-pressure polyethylene (HPLD) excellent in the moldability or anethylene-based polymer differing in the molecular weight or density hasbeen blended to improve the melting characteristics or solid physicalproperties (see, for example, Patent Documents 1 to 3).

Such a blend (ethylene-based resin composition) may satisfy themoldability but has a problem that reduction in the impact strength maybe caused due to blending of HPLD or the molecular weight distributionor copolymerization composition distribution may be broadened to worsenthe transparency.

Also, due to enforcement of the Containers Recycle Law or recent trendof resource saving, the amount of a raw material resin used needs to bereduced and from this standpoint, the demand for reduction in the wallthickness of a molded product is increasing, but in order to reduce thewall thickness, the stiffness (modulus) as well as the impact strengthmust be improved.

As the method for improving the impact strength, a method of reducingthe density of the ethylene-based polymer is well known, but this methodis disadvantageous in that the stiffness is also reduced (the polymerbecomes soft), and for the purpose of reducing the wall thickness, therehas been made, for example, an attempt to use a three-component blendcomposition obtained by further adding a specific HPLD to a combinationof two kinds of specific ethylene.α-olefin copolymers differing in thedensity so as to enhance the moldability or transparency (see, forexample, Patent Document 4).

According to this method, a polyethylene resin composition moreexcellent in the balance between impact strength and stiffness and alsoin the transparency than conventional compositions may be obtained, butthe impact strength is unavoidably reduced due to blending of HPLD andfurthermore, from the standpoint of stably supplying a product ofconstant quality in industrial level, a blend of three kinds ofethylene-based polymers is considered to be economically disadvantageousas compared with conventional compositions.

On the other hand, as to the method for improving the moldability, anattempt to introduce a long-chain branched structure capable ofincreasing the melt viscosity into an ethylene-based polymer has beenmade, but since the design for optimizing the long-chain branchedstructure is insufficient, reduction in the strength or transparencystill cannot be avoided and the improvement level of moldability is yetlow (see, for example, Patent Documents 5 to 8).

The polyolefin produced using a metallocene catalyst for olefinpolymerization has a high uniformity in the polymer molecular structuresuch as molecular weight distribution or copolymerization compositiondistribution and is excellent in various mechanical properties such asimpact strength and long lifetime and therefore, the amount used thereofis recently increasing. The metallocene-based polyolefin is excellent invarious mechanical properties but, because of its narrow molecularweight distribution, is poor in the characteristics important to moldingof a polyolefin, such as melt tension and melt flowability, and cannotsatisfy sufficient performance in terms of mold processing.

As the method for improving the insufficient mold processability of themetallocene-based polyolefin, a method where the melt viscosity isincreased by introducing a long-chain branch into a polyethylene by apolymerization reaction using a specific metallocene complex and theflowability or melt tension is thereby improved, is well known (see, forexample, Patent Document 9). With respect to the specific metallocenecomplex for introducing a long-chain branch, a method using a bridgedbisindenyl complex (see, for example, Patent Documents 10 to 13) or aconstrained geometry half-metallocene complex (see, for example, PatentDocument 14) is well known, but the long-chain branch obtained by such amethod does not develop as in the structure of HPLD, and the improvementof melt viscosity of the polymer is not sufficient.

Also, as to the method for introducing a long-chain branch by ametallocene complex other than those described above, a method forproducing a long-chain branch-containing polyethylene by using a bridgedmetallocene catalyst having a specific structure is known (see, forexample, Patent Document 15), and specifically, an example ofsimultaneously using two kinds of metallocene complexes ofdimethylsilylbis(pentadienyl)zirconium dichloride anddiphenylmethylene(cyclopentadienyl)(fluorenyl)zirconium dichloride isshown. As the improved technology thereof, furthermore, a catalyst wherethe above-described two kinds of complexes are co-supported on the samesupport (see, for example, Patent Documents 16 to 18), and a catalystwhere the kind of the complex combined is improved (see, for example,Patent Documents 19 and 20), are known. In these methods, it is supposedthat one kind of a complex produces a polymer having a polymerizabledouble bond at the terminal (so-called macromer) and another complex isa complex excellent in the copolymerizability and copolymerizes with themacromer to form a long-chain branched structure.

Such a method may achieve introduction of a branched structure that issomewhat more developed than the long-chain branched structure by theconventional metallocene complex, but the level of development is stillinsufficient or those two kinds of metallocene complexes greatly differin the copolymerizability of a comonomer, giving rise to a problem thatthe copolymerization composition distribution of the produced polymermay be broadened or the mechanical properties may deteriorate inassociation with production of a low-melting-point polymer.

Patent Document 21 has reported that when homopolymerization of ethyleneis performed according to solution polymerization by using an asymmetricmetallocene in which a cyclopentadienyl group and an indenyl group arecarbon-bridged and methylaluminoxane, a branch-containing polyethylenecan be produced, but the carbon number indicative of the branch lengthis from 1 to 20. Thus, the branch length is too short to exert an effectof improving mold processability as a long-chain branch, failing inexhibiting strain hardening of the elongational viscosity.

Also, Patent Document 22 has reported polymerization of propylene by apolymerization catalyst prepared by combining an asymmetric metallocenecompound in which a cyclopentadienyl group and an indenyl group, eachhaving a specific substituent, are bridged, with methylaminoxane, butthis document is silent on the possibility of producing a long-chainbranch when the polymerization above is applied to polymerization ofethylene, and the effect of improving the mold processability cannot beexpected.

Furthermore, Patent Document 23 has reported a catalyst system capableof producing an ethylene polymer and an ethylene/butene copolymer, whichare useful as a macromonomer, by using, out of asymmetric metallocenesin which a cyclopentadienyl group and an indenyl group aresilicon-bridged, a metallocene having a methyl group on the 2-, 4- and7-positions of the indenyl group and a modified clay compound, but thenumber of terminal double bonds of the polymer is small, and thisdocument is silent on the possibility of producing a long-chain branchby this catalyst alone.

Recently, the present inventors have reported in Patent Document 24 amethod for producing an ethylene-based polymer improved in the moldprocessability by using a supported catalyst for olefin polymerizationcomprising, as an essential component, out of asymmetric metallocenes inwhich a cyclopentadienyl group and an indenyl group are bridged by abridging group, a specific asymmetric metallocene having no substituentexcept for the bridging group on the cyclopentadienyl group and having ahydrogen atom or a specific substituent on the 3-position of the indenylgroup. According to this method, an ethylene-based polymer having alarge degree of strain hardening of the elongational viscosity isobtained and therefore, the mold processability is improved as comparedwith the conventional long-chain branched polyethylene, but since thelong-chain branching index does not reach that of a high-pressurelow-density polyethylene, more improvement of the long-chain branchedstructure is demanded.

Under these circumstances, it is required to solve the problems of theconventional ethylene-based resin composition and develop apolyethylene-based resin composition excellent in the moldability andcapable of producing a molded product excellent in the balance betweenimpact strength and stiffness as well as in the transparency.Furthermore, in order to solve the problems of a long-chainbranch-containing polyethylene in conventional techniques and improvethe mold processability of a metallocene-based polyethylene, it isrequired to develop an ethylene-based polymer having introducedthereinto a sufficiently large number of appropriate-length long-chainbranches, an olefin polymerization catalyst excellent in theintroduction of long-chain branch, and a production method of anolefin-based polymer.

BACKGROUND ART LITERATURE Patent Document

Patent Document 1: JP-A-7-149962 (the term “JP-A” as used herein meansan “unexamined published Japanese patent application”)

Patent Document 2: JP-A-9-31260

Patent Document 3: JP-A-2006-312753

Patent Document 4: JP-A-2010-31270

Patent Document 5: International Publication No. 97/10295

Patent Document 6: JP-A-2006-63325

Patent Document 7: JP-A-2006-124567

Patent Document 8: JP-A-2007-197722

Patent Document 9: JP-A-2-276807

Patent Document 10: JP-A-8-48711

Patent Document 11: JP-A-8-311260

Patent Document 12: JP-A-2004-149760

Patent Document 13: JP-A-2004-217924

Patent Document 14: JP-A-6-306121

Patent Document 15: JP-A-7-252311

Patent Document 16: JP-A-2006-233208

Patent Document 17: JP-A-2006-321991

Patent Document 18: JP-T-2007-520597 (the term “JP-T” as used hereinmeans a published Japanese translation of a PCT patent application)

Patent Document 19: JP-T-2002-515521

Patent Document 20: JP-A-2009-144148

Patent Document 21: JP-A-5-043619

Patent Document 22: JP-A-7-224079

Patent Document 23: JP-A-2008-050278

Patent Document 24: JP-A-2011-137146

SUMMARY OF THE INVENTION Problems that the Invention is to Solve

An object of the present invention is, considering the above-describedproblems of conventional techniques, to provide an ethylene-basedpolymer improved in the mold processability. Another object of thepresent invention is, considering the above-described problems ofconventional techniques, to provide a polyethylene-based resincomposition excellent in the molding characteristics and at the sametime, excellent in the balance between impact strength and stiffness aswell as in the transparency; provide a molded product excellent in thebalance between impact strength and stiffness and also in thetransparency, which is obtained by the injection molding,compression-injection molding, rotational molding, extrusion molding,hollow molding, blow molding or inflation molding of thepolyethylene-based resin composition; and provide use of the moldedproduct. Still another object of the present invention is to provide anolefin polymerization catalyst component capable of producing ametallocene-based polyolefin or a metallocene-based polyethylene, inwhich a sufficiently large number of appropriate length long-chainbranches are introduced so as to improve the mold processability of ametallocene-based polyolefin, particularly a metallocene-basedpolyethylene; an olefin polymerization catalyst containing thecomponent; and a method for producing an olefin-based polymer by usingthe catalyst.

Incidentally, in the present invention, the polyethylene is a generalterm of an ethylene homopolymer and a copolymer of ethylene and thelater-described olefin and can be restated as an ethylene-based polymer.

Means for Solving the Problems

As a result of a number of intensive studies to attain theabove-described objects, the present inventors have found that when aspecific ethylene-based polymer having a small amount of long-chainbranched structure characterized by the elongational viscosity behaviorand a specific ethylene-based polymer having a specific long-chainbranched structure similarly characterized by the elongational viscositybehavior are combined and these two polymers are blended to give aspecific MFR and a specific density, the obtained polyethylene-basedresin composition exhibits good characteristics capable of solving theabove-described problems. The present inventors have been accomplishedbased on this finding.

That is, according to a first aspect of the present invention, anethylene-based polymer satisfying the following condition (B-1′) tocondition (B-6) is provided.

(B-1′) MFR_(B)=0.001 to 200 g/10 min,

(B-2″) Density_(B)=0.880 to 0.970 g/cm³,

(B-3) [Mw/Mn]_(B)=2.0 to 10.0,

(B-4) in a double logarithmic plot of elongational viscosity η(t) (unit:Pa·sec) and elongation time t (unit: sec) measured at a temperature of170° C. and an elongational strain rate of 2 (unit: l/sec), aninflection point of the elongational viscosity attributable to strainhardening is not observed, or when the inflection point is observed,assuming that the maximum elongational viscosity after strain hardeningis η_(B;Max)(t₁) and the approximate straight line of the elongationalviscosity before hardening is η_(B;Linear)(t), the degree of strainhardening [λmax(2.0)]_(B) defined by η_(B;Max)(t₁)/η_(B;Linear)(t₁) isfrom 1.2 to 30.0,

(B-5) the ratio [λmax(2.0)]_(B)/[λmax(0.1)]_(B) of [λmax(2.0)]_(B)defined in the same manner as in the condition (B-4′) and[λmax(0.1)]_(B) measured similarly by setting the elongational strainrate to 0.1 (unit: l/sec) is from 1.2 to 10.0, and

(B-6) the polymer is produced by an ethylene polymerization reactionusing a transition metal-containing catalyst.

According to a second aspect of the present invention, theethylene-based polymer in the first aspect of the present invention,further satisfying at least one of the following condition (B-7) andcondition (B-8) is provided:

(B-7) the branching index (g_(C)′) at a molecular weight of 1,000,000 asmeasured by a GPC measurement apparatus combining a differentialrefractometer, a viscosity detector and a light scattering detector isfrom 0.30 to 0.70, and

(B-8) the content (W_(C)) of components having a molecular weight of1,000,000 or more as measured by a GPC measurement apparatus combining adifferential refractometer, a viscosity detector and a light scatteringdetector is from 0.01 to 30%.

According to a third aspect of the present invention, apolyethylene-based resin composition comprising: (A) from 41 to 99 wt %of an ethylene-based polymer satisfying the following condition (A-1) tocondition (A-4); and (B) from 1 to 59 wt % of the ethylene-based polymerclaimed in claim 1 or 2, wherein MFR of the composition as a whole isfrom 0.05 to 50 g/10 min and the density is from 0.910 to 0.960 g/cm³,is provided:

Conditions of Ethylene-Based Polymer (A):

(A-1) MFR_(A)=0.3 to 100 g/10 min,

(A-2) Density_(A)=0.915 to 0.970 g/cm³,

(A-3) [Mw/Mn]_(A)=2.0 to 10.0, and

(A-4) in a double logarithmic plot of elongational viscosity η(t) (unit:Pa·sec) and elongation time t (unit: sec) measured at a temperature of170° C. and an elongational strain rate of 2 (unit: l/sec), aninflection point of the elongational viscosity attributable to strainhardening is not observed, or when the inflection point is observed,assuming that the maximum elongational viscosity after strain hardeningis η_(A;Max)(t₁) and the approximate straight line of the elongationalviscosity before hardening is η_(A;Linear)(t), the degree of strainhardening [λmax(2.0)]_(A) defined by η_(A;Max)(t₁)/η_(A;Linear)(t₁) isfrom 1.0 to 2.0.

According to a fourth aspect of the present invention, thepolyethylene-based resin composition in the the third aspect of thepresent invention, wherein said ethylene-based polymer (B) satisfies thefollowing condition (B-1) to condition (B-6), is provided:

Conditions of Ethylene-Based Polymer (B):

(B-1) MFR_(B)=0.01 to 1.5 g/10 min and 100>MFR_(A)/MFR_(B)>1.0,

(B-2) Density_(B)=0.880 to 0.940 g/cm³,

(B-3) [Mw/Mn]_(B)=2.0 to 10.0,

(B-4) [λmax(2.0)]_(B) defined in the same manner as in the condition(A-4) of the third aspect of the present invention is from 1.2 to 20.0and 20>[λmax(2.0)]_(B)[λmax(2.0)]_(A)>1.0,

(B-5) the ratio [λmax(2.0)]_(B)/[λmax(0.1)]_(B) of [λmax(2.0)]_(B)defined in the same manner as in the condition (A-4) of the third aspectof the present invention and [λmax(0.1)]_(B) measured similarly bysetting the elongational strain rate to 0.1 (unit: l/sec) is from 1.2 to10.0, and

(B-6) the polymer is produced by an ethylene polymerization reactionusing a transition metal-containing catalyst.

According to a fifth aspect of the present invention, thepolyethylene-based resin composition in the the third aspect of thepresent invention, wherein said ethylene-based polymer (B) furthersatisfies the following condition (B-2′), is provided:

(B-2′) 1.070>density_(A)/density_(B)>0.990.

According to a sixth aspect of the present invention, thepolyethylene-based resin composition in the the third aspect of thepresent invention, wherein said ethylene-based polymer (A) is anethylene polymer or ethylene.α-olefin copolymer produced byhomopolymerization of ethylene or copolymerization with an α-olefincaused by a Ziegler-Natta catalyst produced using a magnesium compoundand a titanium compound, is provided.

According to a seventh aspect of the present invention, a molded productobtained by an injection molding, compression-injection molding,rotational molding, extrusion molding, hollow molding or blow molding ofthe polyethylene-based resin composition in the third aspect of thepresent invention, is provided.

According to an eighth aspect of the present invention, a film obtainedby an extrusion molding, hollow molding, blow molding or inflationmolding of the polyethylene-based resin composition in the third aspectof the present invention.

According to a ninth aspect of the present invention, an olefinpolymerization catalyst component comprising the following component(A-1b) and component (A-2b), is provided:

Component (A-1b): a metallocene compound represented by the followingformula (1b):

[in formula (1b), M^(1b) represents any one transition metal of Ti, Zrand Hf; each of X^(1b) and X^(2b) independently represents a hydrogenatom, a halogen atom, a hydrocarbon group having a carbon number of 1 to20, a hydrocarbon group containing an oxygen atom or a nitrogen atom andhaving a carbon number of 1 to 20, a hydrocarbon group-substituted aminogroup having a carbon number of 1 to 20, or an alkoxy group having acarbon number of 1 to 20; each of Q^(1b) and Q^(2b) independentlyrepresents a carbon atom, a silicon atom or a germanium atom; eachR^(1b) independently represents a hydrogen atom or a hydrocarbon grouphaving a carbon number of 1 to 10 and at least two members out of fourR^(1b) may combine to form a ring together with Q^(1b) and Q^(2b); m^(b)is 0 or 1 and when m^(b) is 0, Q^(1b) is bonded directly to theconjugated 5-membered ring including R^(2b) and R^(3b); and each ofR^(2b), R^(3b) and R^(4b) independently represents a hydrogen atom, ahalogen atom, a hydrocarbon group having a carbon number of 1 to 20, asilicon-containing hydrocarbon group containing from 1 to 6 silicons andhaving a carbon number of 1 to 18, a halogen-containing hydrocarbongroup having a carbon number of 1 to 20, a hydrocarbon group containingan oxygen atom or a sulfur atom and having a carbon number of 1 to 40,or a silyl group substituted with a hydrocarbon group having a carbonnumber of 1 to 40 and out of R^(2b), R^(3b) and R^(4b), only either onepair of adjacent R^(3b) and R^(3b) and adjacent R^(2b) and R^(3b) mayform a ring together with the carbon atoms to which the pair is bonded],and

Component (A-2b): a metallocene compound represented by the followingformula (2b):

[in formula (2b), M^(2b) represents any one transition metal of Ti, Zrand Hf; each of X^(11b) and X^(12b) independently represents a hydrogenatom, a halogen atom, a hydrocarbon group having a carbon number of 1 to20, a hydrocarbon group containing an oxygen atom or a nitrogen atom andhaving a carbon number of 1 to 20, a hydrocarbon group-substituted aminogroup having a carbon number of 1 to 20, or an alkoxy group having acarbon number of 1 to 20, Q^(11b) represents a carbon atom, a siliconatom or a germanium atom; each R^(11b) independently represents ahydrogen atom or a hydrocarbon group having a carbon number of 1 to 10and two R^(11b) may combine with each other to form a ring together withQ^(11b); each of R^(12b), R^(14b) and R^(15b) independently representsan atom or a group selected from a hydrogen atom, a halogen atom, ahydrocarbon group having a carbon number of 1 to 20, asilicon-containing hydrocarbon group containing from 1 to 6 silicons andhaving a carbon number of 1 to 18, a halogen-containing hydrocarbongroup having a carbon number of 1 to 20, a hydrocarbon group containingan oxygen atom or a sulfur atom and having a carbon number of 1 to 40,and a silyl group substituted with a hydrocarbon group having a carbonnumber of 1 to 40, provided that at least one member is not a hydrogenatom; each R^(13b) independently represents a hydrocarbon group having acarbon number of 1 to 20, a silicon-containing hydrocarbon groupcontaining from 1 to 6 silicons and having a carbon number of 1 to 18, ahalogen-containing hydrocarbon group having a carbon number of 1 to 20,a hydrocarbon group containing an oxygen atom or a sulfur atom andhaving a carbon number of 1 to 40, or a silyl group substituted with ahydrocarbon group having a carbon number of 1 to 40; and out of R^(12b),R^(13b), R^(14b) and R^(15b), any only one pair of adjacent R^(12b) andR^(12b), adjacent R^(13b) and R^(13b) and adjacent R^(12b) and R^(13b)and any only one pair of adjacent R^(14b) and R^(14b), adjacent R^(15b)and R^(15b) and adjacent R^(14b) and R^(15b) may form a ring togetherwith the carbon atoms to which the pair is bonded].

According to a tenth aspect of the present invention, an olefinpolymerization catalyst component comprising a metallocene compoundrepresented by the following formula (1c), is provided:

[in formula (1c), M^(1c) represents any one transition metal of Ti, Zrand Hf; each of X^(1c) and X^(2c) independently represents a hydrogenatom, a halogen atom, a hydrocarbon group having a carbon number of 1 to20, a hydrocarbon group containing an oxygen atom or a nitrogen atom andhaving a carbon number of 1 to 20, a hydrocarbon group-substituted aminogroup having a carbon number of 1 to 20, or an alkoxy group having acarbon number of 1 to 20; each of Q^(1c) and Q^(2c) independentlyrepresents a carbon atom, a silicon atom or a germanium atom; eachR^(1c) independently represents a hydrogen atom or a hydrocarbon grouphaving a carbon number of 1 to 10 and at least two members out of fourR^(1c) may combine to form a ring together with Q^(1c) and Q^(2c); m^(c)is 0 or 1 and when m^(c) is 0, Q^(1c) is bonded directly to theconjugated 5-membered ring including R^(2c); each of R^(2c) and R^(4c)independently represents a hydrogen atom, a halogen atom, a hydrocarbongroup having a carbon number of 1 to 20, a silicon-containinghydrocarbon group containing from 1 to 6 silicons and having a carbonnumber of 1 to 18, a halogen-containing hydrocarbon group having acarbon number of 1 to 20, a hydrocarbon group containing an oxygen atomand having a carbon number of 1 to 20, or a hydrocarbongroup-substituted silyl group having a carbon number of 1 to 20; andR^(3c) represents a substituted aryl group represented by the followingformula (1-ac)]:

[in formula (1-ac), Y^(1c) represents an atom of Group 14, Group 15 orGroup 16 of the periodic table; each of R^(5c), R^(6c), R^(7c), R^(8c)and R^(9c) independently represents a hydrogen atom, a fluorine atom, achlorine atom, a bromine atom, a hydrocarbon group having a carbonnumber of 1 to 20, a hydrocarbon group containing oxygen or nitrogen andhaving a carbon number of 1 to 20, a hydrocarbon group-substituted aminogroup having a carbon number of 1 to 20, an alkoxy group having a carbonnumber of 1 to 20, a silicon-containing hydrocarbon group containingfrom 1 to 6 silicons and having a carbon number of 1 to 18, ahalogen-containing hydrocarbon group having a carbon number of 1 to 20,or a hydrocarbon group-substituted silyl group having a carbon number of1 to 20; adjacent groups of R^(5c), R^(6c), R^(7c), R^(8c) and R^(9c)may combine with each other to form a ring together with the atomsbonded to these groups; n^(c) is 0 or 1 and when n^(c) is 0, thesubstituent Rx is not present on Y^(1c); and p^(c) is 0 or 1 and whenp^(c) is 0, the carbon atom to which R^(7c) is bonded and the carbonatom to which R^(9c) is bonded are bonded directly; provided that whenY^(1c) is a carbon atom, at least one of Rx, R⁶, R^(7c), R^(8c) andR^(9c) is not a hydrogen atom].

According to an eleventh aspect of the present invention, an olefinpolymerization catalyst comprising the olefin polymerization catalystcomponent in the ninth or tenth aspect of the present invention, isprovided.

According to a twelfth aspect of the present invention, a productionmethod of an ethylene-based polymer, comprising producing anethylene-based polymer satisfying at least the condition (B-4) among theconditions in the first aspect of the present invention by using anolefin polymerization catalyst containing the following components (A)and (B), is provided:

Component (A): at least any one of the following catalyst components(A-i) to (A-iii):

(A-i) the olefin polymerization catalyst component in the ninth aspectof the present invention,

(A-ii) the olefin polymerization catalyst component in the tenth aspectof the present invention, and

(A-iii) an olefin polymerization catalyst component containing ametallocene compound represented by the following formula (1d):

[in formula (1d), M^(1d) represents any one transition metal of Ti, Zrand Hf; each of X^(1d) and X^(2d) independently represents a hydrogenatom, a halogen atom, a hydrocarbon group having a carbon number of 1 to20, a hydrocarbon group containing an oxygen atom or a nitrogen atom andhaving a carbon number of 1 to 20, a hydrocarbon group-substituted aminogroup having a carbon number of 1 to 20, or an alkoxy group having acarbon number of 1 to 20; each of Q^(1d) and Q^(2d) independentlyrepresents a carbon atom, a silicon atom or a germanium atom; eachR^(1d) independently represents a hydrogen atom or a hydrocarbon grouphaving a carbon number of 1 to 10 and at least two members out of fourR^(1d) may combine to form a ring together with Q^(1d) and Q^(1d); m^(d)is 0 or 1 and when m^(d) is 0, Q^(1d) is bonded directly to theconjugated 5-membered ring including R^(2d) and R^(3d); each of R^(2d)and R^(3d) represents a hydrogen atom, a halogen atom, a hydrocarbongroup having a carbon number of 1 to 20, a silicon-containinghydrocarbon group containing from 1 to 6 silicons and having a carbonnumber of 1 to 18, a halogen-containing hydrocarbon group having acarbon number of 1 to 20, a hydrocarbon group containing an oxygen atomand having a carbon number of 1 to 20, or a hydrocarbongroup-substituted silyl group having a carbon number of 1 to 20,provided that at least one R^(2d) is not a hydrogen atom; R^(4d)represents a saturated or unsaturated divalent hydrocarbon group havinga carbon number of 4 or 5 for forming a condensed ring with the5-membered ring to which R^(4d) is bonded: R^(5d) is an atom or a groupbonded to a carbon atom of R^(4d) and each independently represents ahydrogen atom, a halogen atom, a hydrocarbon group having a carbonnumber of 1 to 20, a silicon-containing hydrocarbon group containingfrom 1 to 6 silicons and having a carbon number of 1 to 18, ahalogen-containing hydrocarbon group having a carbon number of 1 to 20,a hydrocarbon group containing an oxygen atom and having a carbon numberof 1 to 20, or a hydrocarbon group-substituted silyl group having acarbon number of 1 to 20; and n^(d) represents an integer of 0 to 10 andwhen n^(d) is 2 or more, at least two R^(5d) may form a ring togetherwith the carbon atoms to which R^(5d) are bonded], and

Component (B): a compound capable of reacting with a metallocenecompound of the component (A) to produce a cationic metallocenecompound.

According to a thirteenth aspect of the present invention, theethylene-based polymer in the first aspect of the present invention,which is produced by the production method of an ethylene-based polymerin the twelfth aspect of the present invention, is provided.

According to a fourteenth aspect of the present invention, thepolyethylene-based resin composition in the third aspect of the presentinvention, wherein said ethylene-based polymer is the ethylene-basedpolymer in the thirteenth aspect of the present invention, is provided.

Advantage of the Invention

According to the present invention, an ethylene-based polymer having adeveloped long-chain branched structure and excellent in the moldabilitycan be provided.

The polyethylene-based resin composition of the present invention hasexcellent molding characteristics and at the same time, has an effectthat the balance between impact strength and stiffness is excellent andfurthermore, the transparency is excellent. In addition, the moldedproduct by the injection molding, compression-injection molding,rotational molding, extrusion molding, hollow molding, blow molding orinflation molding of the polyethylene-based resin composition is alsoexcellent in the balance between impact strength and stiffness as wellas in the transparency, so that a molded product reduced in the wallthickness can be provided in an industrially advantageous manner.

Moreover, according to the present invention, a method for producing ametallocene-based polyolefin or metallocene-based polyethylene having asufficiently large number of appropriate-length long-chain branches,wherein an olefin polymerization catalyst component containing aspecific metallocene compound is prepared and the catalyst component isused for an olefin polymerization catalyst, can be provided. In turn, amethod for improving the mold processability of a metallocene-basedpolyethylene can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph showing a base line and a section of a chromatogramused in the gel permeation chromatography (GPC) method.

FIG. 2 is a plot diagram of the elongational viscosity when aninflection point of elongational viscosity is observed (a typicalexample of the ethylene-based polymer (B) in Examples).

FIG. 3 is a plot diagram of the elongational viscosity when aninflection point of elongational viscosity is not observed (a typicalexample of the ethylene-based polymer (A) in Examples).

FIG. 4A is a molecular weight distribution curve calculated from theGPC-VIS measurement (branched structure analysis), and FIG. 4B is agraph showing the relationship between the branching index (g′) and themolecular weight (M).

MODE FOR CARRYING OUT THE INVENTION

The present invention relates to a polyethylene-based resin compositionobtained by blending a specific ethylene-based polymer (A) having asmall amount of long-chain branched structure characterized by theelongational viscosity behavior and a specific ethylene-based polymer(B) having a specific long-chain branched structure similarlycharacterized by the elongational viscosity behavior to give a specificMFR and a specific density; a molded product obtained by molding thepolyethylene-based resin composition; and use of the molded product. Thepresent invention is described below item by item.

[I] Polyethylene-Based Resin Composition of the Present Invention

The polyethylene-based resin composition of the present invention ischaracterized by containing from 41 to 99 wt % of (A) an ethylene-basedpolymer satisfying specific conditions (A-1) to (A-4) (hereinafter,sometimes simply referred to as component (A)) and from 1 to 59 wt % of(B) an ethylene-based polymer satisfying specific conditions (B-1) to(B-6) (hereinafter, sometimes simply referred to as component (B)),wherein MFR of the composition as a whole is from 0.05 to 50 g/10 minand the density is from 0.910 to 0.960 g/cm³. Respective componentsconstituting the polyethylene-based resin composition of the presentinvention, characteristics thereof, and the like are described below.

(1) Ethylene-Based Polymer (A)

The compound (A) that is one of components constituting thepolyethylene-based resin composition of the present invention satisfiesall of the conditions (A-1) to (A-4) described below.

1-1. Condition (A-1)

The melt flow rate (MFR_(A)) of the component (A) in the presentinvention is from 0.3 to 100 g/10 min, preferably from 0.9 to 20 g/10min, more preferably from 1.4 to 10 g/10 min.

If MFR_(A) is less than 0.3 g/10 min, the polyethylene-based resincomposition may be inferior in the moldability, particularly in the meltflowability and spreadability, and if MFR_(A) exceeds 100 g/10 min, thepolyethylene-based resin composition or its molded product may bedisadvantageously reduced in the mechanical strength such as impactstrength, tear strength and tensile strength. Incidentally, in thepresent invention. MFR of the ethylene-based polymer andpolyethylene-based resin composition indicates a value when measuredunder the conditions of 190° C. and a load of 21.18 N (2.16 kg) inaccordance with “Test Method for Melt Flow Rate (MFR) and Melt VolumeFlow Rate (MVR) of Plastics-Thermoplastics” of JIS K7210.

1-2. Condition (A-2)

The density_(A) of the ethylene-based polymer (A) in the presentinvention is from 0.915 to 0.970 g/cm³, preferably from 0.917 to 0.950g/cm³, more preferably from 0.925 to 0.940 g/cm³.

When the density_(A) is in this range, the polyethylene-based resincomposition or its molded product is excellent in the balance betweenimpact strength and stiffness and in the transparency. On the otherhand, if the density_(A), is less than 0.915 g/cm³, the stiffness isreduced and when the product is a molded product having a smallthickness, such as film and sheet, as well as various problems in usingthe product, a problem is disadvantageously brought about in the step ofwinding up the product or the post-processing step such as surfaceprinting•lamination or when the product is a molded product having alarge wall thickness, such as pipe and various containers, since theproduct is too soft and undergoes deformation, the wall thickness mustbe disadvantageously designed to be larger than necessary. Also, if thedensity_(A) exceeds 0.970 g/cm³, the impact strength or transparency isdeteriorated and this is not preferred. Incidentally, in the presentinvention, the density of the ethylene-based polymer or thepolyethylene-based resin composition indicates a value when measured bythe following method.

Pellets are hot-pressed to prepare a 2 mm-thick press sheet, and thissheet is placed in a beaker having a volume of 1,000 ml. The beaker isfilled with distilled water, covered with a watch glass, heated by amantle heater and after coming to a boil, the distilled water was boiledfor 60 minutes. Thereafter, the beaker is placed on a wooden table andallowed to cool. In this operation, the amount of the boiling distilledwater after boiling for 60 minutes is set to 500 ml, and the period oftime until reaching room temperature is adjusted not to fall below 60minutes. Furthermore, the test sheet is immersed in a nearly centralpart of the water while keeping it away from contact with the beaker orwater surface. The sheet is annealed for 16 to 24 hours under theconditions of 23° C. and a humidity of 50%, then punched into 2-mmsquares, and measured at a test temperature of 23° C. in accordance with“Test Method for Density and Specific Gravity of Plastics-UnfoamablePlastics” of JIS K7112.

1-3. Condition (A-3)

The ratio ([Mw/Mn]_(A)) between weight average molecular weight (Mw) andnumber average molecular weight (Mn) of the component (A) in the presentinvention is from 2.0 to 10.0, preferably from 2.5 to 10.0, morepreferably from 2.9 to 5.0. If [Mw/Mn]_(A) is less than 2.0, thepolyethylene-based resin composition may be inferior in the moldability,particularly in the melt flowability, or the polymer may be difficult tomix with other polymer components and therefore, this should be avoided.

If [Mw/Mn]_(A) exceeds 10.0, the effect of improving the stiffness ofthe polyethylene-based resin composition or its molded product may beinsufficient or the transparency may be deteriorated, and this is notpreferred. Incidentally, in the present invention, each of Mw and Mn ofthe ethylene-based polymer or polyethylene-based resin compositionindicates a value measured by gel permeation chromatography (GPC)method.

Conversion to molecular weight from retention volume is performed usinga calibration curve prepared in advance with standard polystyrene. Allof standard polystyrenes used are the following brands of TosohCorporation: F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500and A1000.

The calibration curve is prepared by injecting 0.2 mL of a solutionafter dissolving each standard polystyrene in ODCB (containing 0.5 mg/mLof BHT) to have a concentration of 0.5 mg/mL. As the calibration curve,a cubic expression obtained by approximation by the least square methodis employed. For the viscosity expression ([η]=K×M^(α)) used in theconversion to the molecular weight, the following numerical values areused.

PS: K=1.38×10⁻⁴, α=0.7

PE: K=3.92×10⁻⁴, α=0.733

PP: K=1.03×10⁻⁴, α=0.78

Incidentally, the measurement conditions of GPC are as follows.

Instrument: GPC (ALC/GPC, 150C) manufactured by Waters

Detector: IR detector (measurement wavelength: 3.42 μm), MIRAN 1A,manufactured by FOXBORO

Column: AD806M/S (three) manufactured by Showa Denko

Moving phase solvent: o-dichlorobenzene

Measurement temperature: 140° C.

Flow rate: 1.0 ml/min

Injection volume: 0.2 ml

Preparation of sample: A 1 mg/mL solution of the sample is preparedusing ODCB (containing 0.5 mg/mL of BHT) and dissolved over about 1 hourat 140° C.

Incidentally, a base line and a section of the obtained chromatogram aredetermined, for example, as shown in FIG. 1.

1-4. Condition (A-4)

The component (A) in the present invention satisfies the condition thatin a double logarithmic plot of elongational viscosity η(t) (unit:Pa·sec) and elongation time t (unit: sec) measured at a temperature of170° C. and an elongational strain rate of 2 (unit: l/sec), aninflection point of the elongational viscosity attributable to strainhardening is not observed or when the inflection point is observed,assuming that the maximum elongational viscosity after strain hardeningis η_(Max)(t₁) and the approximate straight line of the elongationalviscosity before hardening is η_(Linear)(t), the degree of strainhardening [λmax(2.0)]_(A) defined by η_(Max)(t₁)/η_(Linear)(t₁) is from1.0 to 2.0, preferably from 1.0 to 1.5, more preferably from 1.0 to 1.2,and in a most preferred case, the inflection point is not observed or[λmax(2.0)]_(A) is from 1.0 to 1.1. Here, the approximate straight lineof the elongational viscosity before hardening is a tangent line havinga smallest gradient (here, however, the gradient is 0 or a positivevalue) among tangent lines of a curve of the double logarithmic graph inthe range of t corresponding to a strain amount of 0.2 to 1.0.

If [λmax(2.0)]_(A) is less than 1.0, the ethylene-based polymer,polyethylene-based resin composition or its molded product may be in anon-uniform molten state or may have a thermally unstable structure, andthis is not preferred. If [λmax(2.0)]_(A) exceeds 2.0, the melt tensionand flowability during molding may be excellent, but thepolyethylene-based resin composition or its molded product may bedisadvantageously reduced in the impact strength or transparency.

In general, a polyethylene is processed into an industrial product by ashaping method involving a molten state, such film molding, blow moldingand foam molding, and at this time, the elongational flowcharacteristics represented by the above-described elongationalviscosity or degree of strain hardening greatly affect the ease ofmolding.

That is, a polyethylene having a narrow molecular weight distributionand having no long-chain branch exhibits bad moldability because of itslow melt strength, whereas a polyethylene having an ultrahigh molecularweight component or a long-chain branch component has a property ofundergoing strain hardening during melt elongation, that is, abruptlyrising in the elongational viscosity on the high strain side, and apolyethylene exhibiting this property outstandingly is excellent in themoldability. A polyethylene resin having such elongational flowcharacteristics has an effect of, for example, preventing uneven wallthickness or blown rupture of a product in the film molding or blowmolding, enabling high-speed molding, or making it possible to raise thepercentage of closed pores at the foam molding and provides for meritssuch as increase of strength of a molded article, enhancement of designproperty, reduction in weight, improvement of molding cycle, andelevation of heat insulating property. However, on the other hand, ifthe elongational flow characteristics are too strong, there may arise aproblem, for example, the impact strength of the molded product may bereduced due to strength anisotropy that is presumed to be attributableto molecular orientation during molding, or the transparency may bedeteriorated due to reduction in the surface smoothness of a moldedproduct, which is presumed to be attributable to a property of the meltelasticity being too high.

As a result of intensive studies on a polyethylene-based resincomposition with an attempt to improve the molding process bound up withthe elongational flow characteristics of a polyethylene and overcome theproblem in mechanical properties of a molded product by designing thelong-chain branched structure as a main factor governing theelongational viscosity characteristics, it has been found that, asdescribed above, when an ethylene-based polymer (A) having a smallamount of long-chain branched structure is used as a high MFR maincomponent of the resin composition, that is, as a main component on thelow molecular weight side, the polymer is excellent in contribution toenhancement of mechanical properties, particularly stiffness, andfurthermore, excellent in prevention of deterioration of thetransparency.

With respect to the measurement method for the degree of strainhardening, as long as the uniaxial elongational viscosity can bemeasured, the same value is obtained in principle by any method, anddetails of the measurement method and measurement apparatus aredescribed, for example, in known literature, Polymer, 42 (2001), 8663.

The measurement method and measurement apparatus preferred formeasurement of the ethylene-based polymer of the present inventioninclude the followings.

Measurement Method:

Apparatus: Ares manufactured by Rheometorics

Fixture: Extentional Viscosity Fixture, manufactured by T.A. Instrument

Measurement temperature: 170° C.

Strain rate: 2/sec

Preparation of test piece: A sheet having a size of 18 mm×10 mm and athickness of 0.7 mm is prepared by press molding.

Calculation Method:

The elongational viscosity at 170° C. and a strain rate of 2/sec isplotted in a double logarithmic graph where the abscissa is the time t(sec) and the ordinate is the elongational viscosity η (Pa·sec). On thisdouble logarithmic graph, assuming that the maximum elongationalviscosity until reaching a strain amount of 4.0 after strain hardeningis η_(Max)(t₁) (t₁ is the time at which the maximum elongationalviscosity is shown) and the approximate straight line of theelongational viscosity before hardening is η_(Linear)(t), a valuecalculated as η_(Max)(t₁)/η_(Linear)(t₁) is defined as the degree ofstrain hardening (λmax). Incidentally, occurrence or no occurrence ofstrain hardening is judged by whether an inflection point at which theelongational viscosity is changed from an upwardly projecting curve to adownwardly projecting curve with the elapse of time is present orabsent.

FIGS. 2 and 3 are plot diagrams of typical elongational viscosity. FIG.2 is a case where an inflection point of elongational viscosity isobserved, and η_(Max)(t₁) and η_(Linear)(t) are shown in the figure.FIG. 3 is a case where an inflection point of elongational viscosity isnot observed.

1-5. Composition of Ethylene-Based Polymer (A)

The component (A) in the present invention is an ethylene homopolymer ora copolymer of ethylene and an ca-olefin having a carbon number of 3 to20. Examples of the α-olefin as a copolymerization component used hereinclude propylene, butene-1, 3-methylbutene-1, 3-methylpentene-1,4-methylpentene-1, pentene-1, hexene-1, heptene-1, octene-1, decene-1,tetradecene-1, hexadecene-1, octadecene-1, and eicocene-1. Only one ofthese α-olefins may be used, or two or more thereof may be used incombination. Among these, an α-olefin having a carbon number of 3 to 10is preferred, and specific examples thereof include propylene, butene-1,3-methylbutene-1, 4-methylpentene-1, pentene-1, hexene-1, heptene-1,octene-1, and decene-1. An α-olefin having a carbon number of 4 to 8 ismore preferred, and specific examples thereof include butene-1,3-methylbutene-1, 4-methylpentene-1, pentene-1, hexene-1, heptene-1, andoctene-1. Particularly preferred α-olefins are butene-1, hexene-1, andoctene-1. Incidentally, in the later-described olefin polymerizationcatalyst, even in the case of homopolymerization of ethylene, anα-olefin such as 1-butene and 1-hexene due to an ethyleneoligomerization reaction may occur as a by-product in the polymerizationsystem, or a reaction called “Chain-walking reaction” where ashort-chain branch such as methyl group and ethyl group is produced inthe main chain of an olefin polymer by an isomerization reaction of abond between an active center metal and a terminal carbon at the growthterminal of olefin polymerization, is known, and the short-chainbranched structure produced by such a reaction in the ethylenehomopolymer is sometimes confused with the short-chain branchedstructure produced by copolymerization of an α-olefin.

Accordingly, the ethylene homopolymer as used in the present inventionindicates a polymer produced as a result of polymerization proceededwithout externally supplying an α-olefin as a comonomer, and theethylene.α-olefin copolymer indicates a polymer produced as a result ofpolymerization performed by externally supplying the α-olefin. The term“ethylene-based polymer” is used for collectively referring to theethylene homopolymer and the ethylene-α-olefin copolymer (including thelater-described case of using, as a comonomer, a monomer except for anα-olefin).

The ratio of ethylene and an α-olefin in the ethylene-based polymer isfrom about 80 to 100 wt % of ethylene and from about 0 to 20 wt % of anα-olefin, preferably from about 85 to 99.9 wt % of ethylene and fromabout 0.1 to 15 wt % of an α-olefin, more preferably from about 90 to99.5 wt % of ethylene and from about 0.5 to 10 wt of an α-olefin, stillmore preferably from about 90 to 99 wt % of ethylene and from about 1 to10 wt % of an α-olefin. When the ethylene content is in this range, thepolyethylene-based resin composition or its molded product can have goodbalance between stiffness and impact strength.

The copolymerization may be any of alternate copolymerization, randomcopolymerization and block copolymerization. Of course, it is possibleto use a small amount of a comonomer other than ethylene and anα-olefin, and in this case, the comonomer includes a compound having apolymerizable double bond, for example, styrenes such as styrene,4-methylstyrene and 4-dimethylaminostyrene, dienes such as1,4-butadiene, 1,5-hexadiene, 1,4-hexadiene and 1,7-octadiene, cycliccompounds such as norbornene and cyclopentene, and oxygen-containingcompounds such as hexenol, hexenoic acid and methyl octenoate. However,in the case of using dienes, it is indisputable that the comonomer mustbe used within a range causing no development of a long-chain branchedstructure, that is, within a range satisfying the condition (A-4).

1-6. Production Method of Ethylene-Based Polymer (A)

As the component (A) in the present invention, an ethylene-based polymerhaving the composition above and satisfying all of the conditions (A-1)to (A-4) is produced and used. The production is performed by a methodof homopolymerizing ethylene or copolymerizing ethylene with theabove-described α-olefin, by using an olefin polymerization catalyst.

As the olefin polymerization catalyst, various kinds of catalysts areknown at present, and the catalyst is not limited as long as theethylene-based polymer (A) can be prepared within the limitations of theconfiguration of catalyst components and the design of polymerizationconditions or post-processing conditions, but as an example of thetechnique suitable for the production of the ethylene-based polymer (A)and satisfying the profitability at the industrial level, specificexamples include transition metal-containing catalysts for olefinpolymerization described in the following (i) to (iv).

(i) Ziegler Catalyst

Examples of the olefin polymerization catalyst suitable for theproduction of the ethylene-based polymer (A) include a Ziegler-Nattacatalyst that is an olefin coordination polymerization catalyst composedof a combination of a transition metal compound and an alkyl compound orthe like of a typical metal. Above all, a so-called Mg—Ti type Zieglercatalyst in which a solid catalyst component obtained by loading atitanium compound on a magnesium compound and an organoaluminum compoundare combined (refer, for example, to “Shokubai Katsyou Daijiten(Practical Dictionary of Catalysts): issued by Kogyo Chosakai, 2004” and“Shutsugan Keitou Zu-Olefin Jugo Shokubai no Hensen— (Application FlowChart—History of Olefin Polymerization Catalyst—); issued by JapanInstitute of Invention and Innovation, 1995”) is preferred, because thiscatalyst is inexpensive, highly active and excellent in the suitabilityfor polymerization process.

Among others, an Mg/Ti catalyst supported on an inactive supportmaterial described in JP-A-54-142192 and JP-A-54-148093 is preferred.More specifically, examples thereof include a catalyst obtained by aprocess where a porous silica previously treated with triethylaluminumis impregnated with a uniform mixed solution of a tetrahydrofuransolution of anhydrous MgCl₂ and TiCl₃ or TiCl₄ and then dried to a solidstate, and a catalyst obtained by applying preliminary olefinpolymerization to an Mg/Ti catalyst in the presence of an organoaluminumdescribed in JP-A-63-117019, for example, a preliminarily polymerizedcatalyst obtained by a process where a mixed solution of TiCl₄ andmethylhydrogenpolysiloxane is introduced into a solid component obtainedby the reaction of MgCl₂, Ti(OnBu)₄ and methylhydrogenpolysiloxane andthe obtained catalyst is subjected to preliminary ethylenepolymerization in the presence of triethylaluminum. Other examplesinclude an olefin polymerization catalyst in which a low-valent titaniumatom-containing catalyst component obtained by the reaction of amagnesium.aluminum composite material and a quadrivalent titaniumcompound is combined with an organoaluminum compound, described inJP-A-60-195108; a solid-state catalyst obtained by adding dropwiseethylaluminum sesquichloride or the like to a uniform mixture ofmagnesium ethoxide, tri-n-butoxy monochloroethane and n-butanol,described in JP-A-56-61406 and the like; and an olefin polymerizationsolid catalyst containing magnesium, a halogen atom, titanium and anelectron donor, described in JP-A-2001-139635 and the like.

(ii) Metallocene Catalyst

As an example of the polymerization catalyst suitable for the productionof the ethylene-based polymer (A), a metallocene catalyst that is anolefin polymerization catalyst composed of a metallocene-basedtransition metal compound and a promoter component (see, for example,“Metallocene Shokubai ni-yoru Jisedai Polymer Kogyoka Gijutsu(Next-Generation Polymer Engineering Technology by Metallocene Catalyst)(Volume One and Two); issued by Inter-Research, 1994”) is used, becausethis catalyst is relatively inexpensive, highly active and excellent inthe suitability for polymerization process and furthermore, anethylene-based polymer having a narrow molecular weight distribution anda narrow copolymerization composition distribution is obtained.

Among others, an olefin polymerization catalyst system containing aso-called metallocene complex and an alumoxane, described inJP-A-60-35007 and the like, and a catalyst system using a promotercomponent other than alumoxane, described in JP-A-8-34809,JP-A-8-127613, JP-A-11-193306, JP-T-2002-515522 and the like, aresuitably used. As the metallocene complex, those where the center metalis Ti, Zr or Hf belonging to Group 4B of the periodic table exhibit highactivity for ethylene polymerization and therefore, are suitably used.As for the ligand structure of such a center metal, various structuresare known at present and being examined for the polymerizationperformance such as molecular weight of the produced polyethylene andα-olefin copolymerizability. As described above, the ethylene-basedpolymer (A) of the present invention preferably has no or a small amountof long-chain branched structure and for the production of anethylene-based polymer having such a property, a so-called non-bridgedcomplex where a ligand having a conjugated 5-membered ring structure isnot bridged with another ligand by a bridging group, is preferred.

According to the structure classification of metallocene compounds bythe following formulae [1], [2], [3] and [4] described, for example, inJP-A-11-310612, compounds represented by formulae [1] and [3] arepreferred, and a compound represented by formula [1] is more preferred.However, a higher concentration at the polymerization site of ethyleneor α-olefin and a shorter polymerization reaction time are supposed tobe disadvantageous for the production of a long-chain branched structureand therefore, the propriety of the metallocene compound is of courselimited to a relative degree contingent on performing the polymerizationunder the same conditions. In addition, metallocene complexes described,for example, in JP-A-5-132518, JP-A-2000-154196 and JP-A-2004-161760 arealso suitably used. Furthermore, a metallocene complex having aheteroatom-containing monocyclic or polycyclic heteroaromatic group as asubstituent on a ligand of a conjugated 5-membered ring structure,described, for example, in JP-T-2002-535339 is also suitably used.

[wherein each of A¹ to A⁴ represents a ligand having a conjugated5-membered ring structure (A¹ to A⁴ may be the same or different in thesame compound), Q¹ represents a bonding group for bridging twoconjugated 5-membered ring ligands at arbitrary positions, each of Z¹and Z² independently represents a ligand containing a nitrogen, oxygen,silicon, phosphorus or sulfur atom bonded to M, a hydrogen atom, ahalogen atom or a hydrocarbon group, Q² represents a bonding group forbridging Z² and an arbitrary position of the conjugated 5-membered ringligand, M represents a metal atom selected from Group 4 of the periodictable, and each of X and Y independently represents a hydrogen atom, ahalogen atom, a hydrocarbon group, an alkoxy group, an amino group, aphosphorus-containing hydrocarbon group or a silicon-containinghydrocarbon group, which is bonded to M; their details are as defined inthe patent publication above].(iii) Phillips Catalyst

The Phillips catalyst is a chromium catalyst where a chromium compoundis supported on an inorganic oxide support such as silica,silica-alumina and silica-titania and at least a part of chromiumelements supported is converted into a hexavalent chromium element byperforming activation in a non-reducing atmosphere (see, for example, M.P. McDaniel, Advances in Catalysis, Volume 33, page 47, 1985, AcademicPress Inc.; M. P. McDaniel, Handbook of Heterogeneous Catalysis, page2400, 1997, VCH; M. B. Welch et al., Handbook of Polyolefins: Synthesisand Properties, page 21, 1993, Marcel Dekker). The Phillips catalystexhibits high activity for ethylene polymerization and therefore, issuitably used. However, since the ethylene-based polymer produced usinga Phillips catalyst tends to contain a long-chain branched structure orhave a broad molecular weight distribution, its use as theethylene-based polymer (A) of the present invention requires specialcare to satisfy the condition (A-3) or (A-4).

(iv) Post-Metallocene Catalyst

As an example of the polymerization catalyst suitable for the productionof the ethylene-based polymer (A), a post-metallocene catalyst that isan olefin polymerization catalyst using a homogeneous metal complex(non-metallocene complex) except for the above-describedmetallocene-based transition metal compound (see, for example,“Polyethylene Gijutsu Dokuhon (Polyethylene Technology Guidebook; issuedby Kogyo Chosakai Publishing, 2001”, “Kin'itsu-kei Sen'i KinzokuShokubai ni-yoru Living Jugo (Living Polymerization by HomogeneousTransition Metal Catalyst); issued by IPC, 1999”, and “Shokubai KatsuyoDaijiten (Practical Dictionary of Catalysts); issued by Kogyo Chosakai,2004”) is used, because this catalyst is relatively inexpensive andexcellent in the activity and furthermore, an ethylene-based polymerhaving a narrow molecular weight distribution and a narrowcopolymerization composition distribution is obtained.

Among others, suitably used are bisimide, iminoamide and bisamidecompounds of a transition metal having a 4- to 8-membered ring chelatestructure that is formed by bonding a ligand having at least two N atomsto a transition metal belonging to Groups 3 to 11 of the periodic tablethrough those two N atoms and contains the transition metal disclosed,for example, in JP-T-10-513489, JP-T-2002-521538, JP-T-2000-516295,JP-T-2000-514132, Macromolecules, 1996, page 5241, JACS, 1997, 119, page3830, JACS, 1999, 121, page 5798, and Organometallics, 1998, page 3155;bis-hydrocarbyloxy and bis-hydrocarbylthio compounds of a transitionmetal having a 4- to 8-membered ring chelate structure that is formed bybonding a ligand having at least two O or S atoms to a transition metalbelonging to Groups 3 to 11 of the periodic table through those two O orS atoms and contains the transition metal, disclosed, for example, inJP-A-6-136048; iminocarboxylate, thiocarboxylate and phosphinecarboxylate compounds of a transition metal having a 4- to 8-memberedring chelate structure that is formed by bonding a ligand having atleast one N, S or P atom and a carboxyl group (COO) to a transitionmetal belonging to Groups 3 to 11 of the periodic table through the N, Sor P atom and the carboxyl group and contains the transition metal,disclosed, for example, in JP-T-2000-514132, JP-T-2003-535107 andJP-A-2007-77395; β-keto-phosphine, β-keto-imide and β-keto-amidecompounds of a transition metal having a 4- to 8-membered ring chelatestructure that is formed by bonding a ligand having at least one P or Natom and a carbonyl group (CO) to a transition metal belonging to Groups3 to 11 of the periodic table through the P or N atom and the carbonylgroup and contains the transition metal, disclosed, for example, inJP-T-2004-517933; γ-oxy-phosphine, γ-oxy-imide and γ-oxy-amide compoundsof a transition metal having a 4- to 8-membered ring chelate structurethat is formed by bonding a ligand having at least one P or N atom andan O atom to a transition metal belonging to Groups 3 to 11 of theperiodic table through the P or N atom and the O atom and contains thetransition metal, disclosed, for example, in JP-A-64-14217 andJP-T-2004-517933; a γ-sulfonato-phosphine compound of a transition metalhaving a 4- to 8-membered ring chelate structure that is formed bybonding a ligand having at least one P atom and a sulfonic acid residue(SO³) to a transition metal belonging to Groups 3 to 11 of the periodictable through the P atom and the sulfonic acid residue and contains thetransition metal disclosed, for example, in JP-A-6-184214,JP-A-10-195090, JP-T-2002-521534, JP-A-2007-46032 and JP-A-2007-77395;and phenoxyimine and phenoxyamine compounds of a transition metal havinga 4- to 8-membered ring chelate structure that is formed by bonding aligand having at least an N atom and a phenoxy group to a transitionmetal belonging to Groups 3 to 11 of the periodic table through the Natom and an O atom of the phenoxy group and contains the transitionmetal disclosed, for example, in JP-A-11-315109, Chemical Communications(2003), (18), 2272-2273.

As such a non-metallocene complex catalyst, those where the center metalis Ti, Zr, Hf, which belong to Group 4B of the periodic table, V, Cr,Fe, Co, Ni or Pd exhibit high activity and are more suitably used, andthose where the center metal is Ti. Zr, HEf Fe, Ni or Pd are still moresuitably used. However, with some of these post-metallocene catalysts,the ethylene-based polymer produced tends to contain a long-chainbranched structure, contain a short-chain branched structure mainlyconsisting of a methyl branch, or have a broad molecular weightdistribution and therefore, its use as the ethylene-based polymer (A) ofthe present invention requires special care to satisfy the conditions(A-2) to (A-4).

In the present invention, the production of the ethylene-based polymer(A) is preferably performed by contacting ethylene with the olefinpolymerization catalyst of (i) to (iv) above, more preferably with (i) aZiegler catalyst or (ii) a metallocene catalyst, and therebypolymerizing or copolymerizing the ethylene. As the olefinpolymerization catalyst, a plurality of kinds may be selected from (i)to (iv) and used. At the time of performing ethylene polymerization orcopolymerization, any method, for example, a liquid phase polymerizationmethod such as slurry polymerization, solution polymerization, bulkpolymerization in a liquid monomer and suspension polymerization, or agas phase polymerization can be employed. In the case of a slurrypolymerization method, either a slurry polymerization method using apipe loop-type reactor or a slurry polymerization method using anautoclave-type reactor can be used. The industrial polymerizationprocess is described in detail in Kazuo Matsuura and Naotaka Mikami(compilers), “Polyethylene Gijutsu Dokuhon (Polyethylene TechnologyGuidebook)”, page 148, 2001, Kogyo Chosakai Publishing. Thepolymerization method is preferably a slurry polymerization method or agas phase polymerization method, more preferably a gas phasepolymerization method.

The ethylene for use in the present invention may be an ethyleneproduced from a crude oil derived from a normal fossil raw material ormay be a plant-derived ethylene. Also, the polyethylene produced in thepresent invention can be an ethylene-based polymer producing using aplant-derived ethylene. The plant-derived ethylene and the polyethyleneinclude, for example, ethylene and polymers thereof described inJP-T-2010-511634. The plant-derived ethylene or its polymer has aproperty of being carbon neutral (not using a fossil raw material andnot leading to an increase of carbon dioxide in the air) and can providean environment-friendly product.

The liquid phase polymerization method is usually performed in ahydrocarbon solvent. As the hydrocarbon solvent, an inert hydrocarbonsuch as propane, n-butane, isobutane, n-pentane, isopentane, hexane,heptane, octane, decane, cyclohexane, benzene, toluene and xylene isused individually or as a mixture, or a liquid monomer is used. As thegas phase polymerization method, a commonly known polymerization methodusing a fluidized bed, a stirring bed or the like in the co-presence ofan inert gas may be employed, and depending on the case, a so-calledcondensing mode in which a medium for removing the polymerization heatis allowed to coexist can be also employed.

The polymerization temperature is generally from 0 to 300° C.,practically from 50 to 270° C., and although this may vary depending onthe polymerization process employed, preferably, the polymerizationtemperature is from 60 to 110° C. in the slurry polymerization orsuspension polymerization, from 100 to 250° C. in the solutionpolymerization or bulk polymerization in liquid ethylene, and from 60 to100° C. in the gas phase polymerization method. The catalystconcentration and olefin concentration in the reactor may be anarbitrary concentration high enough for allowing the polymerization toproceed. The ethylene concentration may be from about 1 to about 10%based on the weight of the contents of the reactor in the case of slurrypolymerization, suspension polymerization and solution polymerization,and in the case of gas phase polymerization, the concentration may befrom 0.1 to 10 MPa in terms of the total pressure. The polymerizationmay be also performed by causing hydrogen to be present together, andthis is commonly practiced as a method for adjusting MFR of theethylene-based polymer (A). Hydrogen has an effect as a so-called chaintransfer agent for adjusting the molecular weight in general. MFR can beadjusted to a certain extent by changing the polymerization conditionssuch as polymerization temperature and molar ratio of the catalyst. Inorder reduce the amount of the long-chain branch of the ethylene-basedpolymer (A), the ethylene concentration or hydrogen concentration ispreferably higher.

As for the polymerization method, not only single-stage polymerizationof producing an olefin-based polymer by using one reactor but alsomulti-stage polymerization using at least two reactors connected inseries and/or in parallel for increasing the production amount or moreprecisely controlling the molecular weight distribution or comonomercomposition distribution, can be performed. In the case of multi-stagepolymerization, series multi-stage polymerization where a plurality ofreactors are connected and a reaction mixture obtained by polymerizationin a first-stage reactor is continuously fed in sequence to reactors ofsecond and following stages is preferred. In the series multi-stagepolymerization method, a polymerization reaction mixture in the reactorof a precedent stage is continuously discharged and transferred througha connecting pipe to reactors of subsequent and later stages. Also, thepolymerization can be performed even when a so-called scavenger as acomponent for water removal is added to the polymerization system. Asthe scavenger, an organoaluminum compound such as trimethylaluminum,triethylaluminum and triisobutylaluminum, the above-describedorganoaluminum oxy compound, an organozinc compound, or anorganomagnesium compound may be used, but an organoaluminum compound ismost commonly used.

(2) Ethylene-Based Polymer (B)

The compound (B) that is one of components constituting thepolyethylene-based resin composition of the present invention satisfiesall of the conditions (B-1) to (B-6) described below.

2-1. Condition (B-1)

The melt flow rate (MFR_(B)) of the component (B) in the presentinvention is from 0.01 to 1.5 g/10 min, preferably from 0.05 to 1.0 g/10min, more preferably from 0.1 to 0.8 g/10 min.

If MFR_(B) is less than 0.01 g/10 min, the polyethylene-based resincomposition may be inferior in the moldability, particularly in the meltflowability and spreadability, and furthermore, uniform mixing with theethylene-based polymer (A) may be difficult, disadvantageously givingrise to production of an appearance failure such as gel, grain andfisheye or reduction in the impact strength or transparency. If MFR_(B)exceeds 1.5 g/10 min, the effect that the polyethylene-based resincomposition or its molded product may be enhanced in the mechanicalstrength such as impact strength, tear strength and tensile strength aswell as in the transparency may not be sufficiently exerted, and this isnot preferred. In relation to MFR_(A), MFR_(B) must further satisfy100>MFR_(A)/MFR_(B)>1.0 so that the polyethylene-based resin compositionof the present invention or its molded product can be enhanced in themechanical strength such as impact strength, tear strength and tensilestrength and in the transparency, and it is necessary to satisfypreferably 20>MFR_(A)/MFR_(B)>1.1, more preferably15>MFR_(A)/MFR_(B)>1.2, still more preferably 10>MFR_(A)/MFR_(B)>2.0.Incidentally, MFR_(B) indicates a value when measured under the sameconditions as in the condition (A-1).

2-2. Condition (B-2)

The density_(B) of the component (B) in the present invention is from0.880 to 0.940 g/cm³, preferably from 0.891 to 0.940 g/cm³, morepreferably from 0.895 to 0.925 g/cm³, still more preferably from 0.900to 0.915 g/cm³, yet still more preferably from 0.900 to 0.910 g/cm³.

When the density_(B) is in this range, the polyethylene-based resincomposition or its molded product is excellent in the balance betweenimpact strength and stiffness and in the transparency. On the otherhand, if the density_(B) is less than 0.880 g/cm³, the stiffness isreduced and when the product is a molded product having a smallthickness, such as film and sheet, as well as various problems in usingthe product, a problem is disadvantageously brought about in the step ofwinding up the product or the post-processing step such as surfaceprinting•lamination or when the product is a molded product having alarge wall thickness, such as pipe and various containers, since theproduct is too soft and undergoes deformation, the wall thickness mustbe disadvantageously designed to be larger than necessary. In addition,the polymer is heavily sticky even at room temperature and difficult tohandle in the blending step with the ethylene-based polymer (A),disadvantageously giving rise to product sticking of thepolyethylene-based resin composition, and furthermore, the compatibilitywith the ethylene-based polymer (A) may be reduced to deteriorate theimpact strength or transparency due to phase separation. Also, if thedensity_(B) exceeds 0.940 g/cm³, the impact strength or transparency isdeteriorated and this is not preferred.

In relation to the density_(A), the density_(B) preferably satisfies1.070>density_(A)/density_(B)>0.990 so that the polyethylene-based resincomposition of the present invention or its molded product can beenhanced in the mechanical strength such as impact strength, tearstrength and tensile strength and in the transparency, and it isnecessary to satisfy more preferably1.059>density_(A)/density_(B)>1.000, still more preferably1.050>density_(A)/density_(B)>1.005, yet still more preferably1.035>density_(A)/density_(B)>1.010. Incidentally, density_(B) indicatesa value when measured under the same conditions as in the condition(A-2).

2-3. Condition (B-3)

The ratio ([Mw/Mn]_(B)) between weight average molecular weight (Mw) andnumber average molecular weight (Mn) of the component (B) in the presentinvention is from 2.0 to 10.0, preferably from 2.0 to 6.0, morepreferably from 2.5 to 5.6, still more preferably from 2.9 to 4.5, yetstill more preferably from 3.2 to 4.0.

If [Mw/Mn]_(B) is less than 2.0, the polymer may be difficult to mixwith the ethylene-based polymer (A) and therefore, this should beavoided. If [Mw/Mn]_(B) exceeds 10.0, the effect of improving the impactstrength of the polyethylene-based resin composition or its moldedproduct may be insufficient or deterioration of the transparency orsusceptibility to sticking may result, and this is not preferred.Incidentally, [Mw/Mn]_(B) indicates a value when measured under the sameconditions as in the condition (A-3).

2-4. Condition (B-4)

The degree of strain hardening [λmax(2.0)]_(B) of the component (B) inthe present invention is from 1.2 to 20.0, preferably from 1.2 to 10.0,more preferably from 1.7 to 8.0, still more preferably from 2.4 to 6.0,yet still more preferably 3.0 to 5.0.

If [λmax(2.0)]_(B) is less than 1.2, the ethylene-based polymer,polyethylene-based resin composition or its molded product may lack theflowability or melt tension and be deteriorated in the moldingcharacteristics. If [λmax(2.0)]_(B) exceeds 20.0, the flowability andmelt tension may be excellent, but the polyethylene-based resincomposition or its molded product may be disadvantageously reduced inthe impact strength or transparency. Incidentally, [λmax(2.0)]_(B)indicates a value when measured under the same conditions as in thecondition (A-4). Furthermore, as to the relationship of [λmax(2.0)]_(B)and [λmax(2.0)]_(A), when the ratio therebetween satisfies20>[λmax(2.0)]_(B)/[λmax(2.0)]_(A)>1.0, the polyethylene-based resincomposition of the present invention enhanced particularly in thebalance between moldability and mechanical property, and this ispreferred. If the ratio above is 20 or more, the moldability of theresin composition may be improved, but disadvantageously, the mechanicalstrength or transparency may be reduced, or uniform mixing of theethylene-based polymer (A) and the ethylene-based polymer (B) may bedifficult, leading to deterioration of the outer appearance. Also, ifthe ratio is 1.0 or less, the improvement of moldability of the resincomposition may not be sufficiently exerted, and this is not preferred.The ratio is preferably 10>[λmax(2.0)]_(B)/[λmax(2.0)]_(A)>1.1, morepreferably 5.0>[λmax(2.0)]_(B)/[λmax(2.0)]_(A)>1.5, still morepreferably 4.0>[λmax(2.0)]_(B)/[λmax(2.0)]_(A)>1.8.

The effect of the elongational flow characteristics of the polyethyleneon its moldability or mechanical properties of the molded product is asalready described in general terms in the condition (A-4). As a resultof intensive studies on a polyethylene-based resin composition with anattempt to improve the molding process bound up with the elongationalflow characteristics of a polyethylene and overcome the problem inmechanical properties of a molded product by designing the long-chainbranched structure as a main factor governing the elongational viscositycharacteristics, it has been found that when an ethylene-based polymer(A) having a small amount of long-chain branched structure is used as ahigh MFR main component of the resin composition, that is, as a maincomponent on the low molecular weight side and an ethylene-based polymer(B) having a large amount of long-chain branched structure representedby the degree of elongational strain hardening [λmax(2.0)]_(B) definedin the condition (B-4) is used as a low MFR main component of the resincomposition, that is, as a main component on the high molecular weightside, it has been found that as well as enhancement of the moldingcharacteristics, the polyethylene resin composition is excellent in themechanical properties, particularly stiffness and impact strength, andfurthermore, excellent in the transparency. In addition, when thelong-chain branched structure of the ethylene-based polymer (B) hascharacteristics represented by the following condition (B-5) where thestrain rate dependency of the degree of elongational strain hardening isdifferent from that used conventionally, it has been found that theimproving effect is very excellent in all of molding characteristics,mechanical properties and transparency of the polyethylene-based resincomposition.

2-5. Condition (B-5)

As regards the component (B) in the present invention, the ratio[λmax(2.0)]_(B)/[λmax(0.1)]_(B) of [λmax(2.0)]_(B) defined in thecondition (B-4) and [λmax(0.1)]_(B) measured similarly by setting theelongational strain rate to 0.1 (unit: l/sec) is from 1.2 to 10.0,preferably from 1.3 to 5.0, more preferably from 1.4 to 4.0, still morepreferably from 1.5 to 3.0.

If [λmax(2.0)]_(B)/[λmax(0.1)]_(B) is less than 1.2, non-uniform moltenstate of the ethylene-based polymer, polyethylene-based resincomposition or its molded product or thermally unstable structure mayresult or reduction in the impact strength or deterioration of thetransparency may be caused due to strength anisotropy that isattributable to the presence of a significantly elongated long-chainbranched structure, and this is not preferred. If[λmax(2.0)]_(B)/[λmax(0.1)]_(B) exceeds 10.0, the melt tension andflowability during molding may be excellent, but the polyethylene-basedresin composition or its molded product may be disadvantageously reducedin the impact strength or transparency.

2-6. Condition (B-6)

The component (B) in the present invention is a polymer produced by apolymerization reaction using a transition metal-containing catalyst,preferably a polymer produced by an ethylene polymerization reactionusing a transition metal-containing catalyst described in detail laterin 2-10. Production Method of Ethylene-Based Polymer (B) or in [V]Production Method of Ethylene-Based Polymer of the present invention,more preferably a polymer produced by a coordination anionicpolymerization reaction of ethylene using a transition metal-containingcatalyst.

At present, various radical polymerization initiators are well known asthe ethylene polymerization catalyst not containing a transition metal,and specific examples thereof include a peroxide such as dialkylperoxide compound, alkyl hydroperoxide compound, benzoyl peroxide andhydrogen peroxide, and an azo compound such as azobisisobutyronitrileand azobiscyclohexanecarbonitrile. An ethylene-based polymer produced bya radial polymerization reaction using such a radical polymerizationinitiator contains a large amount of long-chain branched structure andwhen used as a component of a polyethylene-based resin composition, thepolymer may exert an effect of enhancing the molding characteristics ortransparency, but the amount of long-chain branched structure becomestoo large to disadvantageously reduce the strength of the composition orits molded product. In addition, realization of enough reducing of theMFR and the density of the ethylene-based polymer (B) or copolymerizingwith a preferred α-olefin may be impossible and in turn, the strength ofthe composition or its molded product cannot be sufficiently increased,which is not preferred. Incidentally, even if the catalyst contains atransition metal, when the polymerization reaction proceedssubstantially by radical polymerization as in a so-called redox systemsuch as hydrogen peroxide/ferrous chloride or cerium salt/alcohol, thecatalyst is not regarded as the transition metal-containing catalyst ofthe present invention.

2-7. Condition (B-7)

As regards the component (B) in the present invention, in addition tothe conditions (B-1) to (B-6), furthermore, the branching index (g_(C)′)at a molecular weight of 1,000,000 as measured by a GPC measurementinstrument with a differential refractometer, a viscosity detector and alight scattering detector is preferably from 0.30 to 0.70. The g_(C)′value is more preferably from 0.30 to 0.59, still more preferably from0.35 to 0.55, yet still more preferably from 0.35 to 0.50. If the g_(C)′value exceeds 0.70, the moldability of the polyethylene-based resincomposition may be insufficient, or the resin composition or its moldedproduct may lack the transparency, and this is not preferred. If theg_(C)′ value is less than 0.30, the moldability of thepolyethylene-based resin composition may be improved, but reduction ofthe impact strength of the molded product or deterioration of thetransparency may disadvantageously result. Incidentally, in the presentinvention, the g_(C)′ value of the ethylene-based polymer or the W_(C)value in the next paragraph is an evaluation technique for the amount oflong-chain branch, using the molecular weight distribution curve orbranching index (g) calculated from the GPC-VIS measurement describedbelow.

2-8. Condition (B-8)

As regards the component (B) in the present invention, in addition tothe conditions (B-1) to (B-7), furthermore, the content (W_(C)) ofcomponents having a molecular weight of 1,000,000 or more as measured bya GPC measurement instrument with a differential refractometer, aviscosity detector and a light scattering detector is preferably from0.01 to 30.0%. The W_(C) value is more preferably from 0.01 to 10.0%,still more preferably from 0.02 to 8.0%, yet still more preferably from0.05 to 6.0%, and most preferably from 0.09 to 4.0%.

If the W_(C) value is less than 0.01%, the polyethylene-based resincomposition may be inferior in the moldability or the resin compositionor its molded product may lack the transparency, and this is notpreferred. If the W_(C) value exceeds 30.0%, the polyethylene-basedresin composition may be enhanced in the melt tension out of themoldability, but the melt flowability may be excessively reduced todisadvantageously cause a problem in the production or molding of theresin composition. Furthermore, the impact strength or the transparencyof the molded product may be deteriorated, and this is not preferred.

[Branched Structure Analysis by GPC-VIS]

As the GPC instrument having a differential refractometer (RI) and aviscosity detector (Viscometer), Alliance GPC V2000 manufactured byWaters was used. Also, as the light scattering detector, a multi-anglelaser light scattering photometer (MALLS), DAWN-E, manufactured by WyattTechnology was used. The detectors were connected in order of MALLS, RIand Viscometer. The mobile phase solvent was 1,2,4-trichlorobenzene(Irganox 1076 as an antioxidant was added at a concentration of 0.5mg/mL). The flow rate was 1 mL/min. Two columns of GMHHR-H(S) HTmanufactured by Tosoh Corporation were connected and used. Thetemperature of each of detectors in the column and the sample injectionpart was 140° C. The sample concentration was set to 1 mg/mL. Theinjection amount (sample loop volume) was 0.2175 mL. In determining theabsolute molecular weight (M) obtained from MALLS, the square radius ofgyration (Rg) and the intrinsic viscosity ([η]) obtained fromViscometer, the data processing software ASTRA (version 4.73.04)attached to MALLS was utilized, and computation was performed byreferring to the following literatures.

REFERENCE LITERATURES

-   1. Developments in polymer characterization. vol. 4. Essex: Applied    Science; 1984. Chapter 1.-   2. Polymer, 45, 6495-6505 (2004)-   3. Macromolecules, 33, 2424-2436 (2000)-   4. Macromolecules, 33, 6945-6952 (2000)    [Calculation of Branching Index (g_(C)′), etc.]

The branching index (g′) is calculated as a ratio (ηbranch/ηlin) betweenthe intrinsic viscosity (ηbranch) obtained by measuring the sample byViscometer and the intrinsic viscosity (ηlin) obtained by separatelymeasuring a linear polymer.

When a long-chain branch is introduced into a polymer molecule, theradius of gyration becomes small as compared with a molecule of a linearpolymer having the same molecular weight, and when the radius ofgyration becomes small, the intrinsic viscosity decreases. Therefore,along with introduction of a long-chain branch, the ratio (ηbranch/ηlin)of the intrinsic viscosity (ηbranch) of a branched polymer to theintrinsic viscosity (ηlin) of a linear polymer having the same molecularweight becomes small. Accordingly, it is meant that when the branchingindex (g′=ηbranch/ηlin) takes a value smaller than 1, a branch isintroduced and as the value becomes smaller, the amount of long-chainbranch introduced is increased. Particularly, in the present invention,the content percentage (%) of components having a molecular weight of1,000,000 or more in terms of the absolute molecular weight obtainedfrom MALLS to the amount of all components measured by RI is calculatedas the content (W_(C)) of components having a molecular weight of1,000,000 or more, and the above-described g′ at a molecular weight of1,000,000 in terms of the absolute molecular weight obtained from MALLSis calculated as g_(C)′.

FIGS. 4A and 4B shown an example of the analysis results by GPC-VISabove. FIG. 4A shows a molecular weight distribution curve measuredbased on the molecular weight (M) obtained from MALLS and theconcentration obtained from RI, and FIG. 4B shows a branching index (g′)at the molecular weight (M). Here, as the linear polymer, a linearpolyethylene, Standard Reference Material 1475a (National Institute ofStandards & Technology), was used.

2-9. Composition of Ethylene-Based Polymer (B)

As for the composition of the component (B) in the present invention,the description in 1-5. Composition of Ethylene-Based Polymer (A) abovecan apply as-is except for the ratio between ethylene and α-olefin, andwith respect to the same portions, description is omitted.

The ethylene-based polymer (B) of the present invention is preferably acopolymer of ethylene and the α-olefin described above in 1-5. and mostpreferably a copolymer with hexene-1 and octene-1. The ratio of ethyleneand the α-olefin in the ethylene-based polymer (B) of the presentinvention is from about 75 to 99.5 wt % of ethylene and from about 0.5to 25 wt % of α-olefin, preferably from about 78 to 97 wt % of ethyleneand from about 3 to 22 wt % of α-olefin, more preferably from about 80to 96 wt % of ethylene and from about 4 to 20 wt % of α-olefin, stillmore preferably from about 82 to 95 wt % of ethylene and from about 5 to18 wt % of α-olefin. When the ethylene content is in this range, thepolyethylene-based resin composition or its molded product has goodbalance between stiffness and impact strength and is excellent also inthe transparency. In the case of using the above-described dienes, thedienes must be of course used in the range where the long-chain branchedstructure satisfies the conditions (B-4) and (B-5).

2-10. Production Method of Ethylene-Based Polymer (B)

As for the production method of the ethylene-based polymer (B) in thepresent invention, the description in 1-6. Production Method ofEthylene-Based Polymer (A) above can apply as-is except that selectionof an olefin polymerization catalyst appropriate to provide for along-chain branched structure corresponding to the conditions (B-4) and(B-5) to the ethylene-based polymer (B) must be taken care of, and withrespect to the same portions, description is omitted.

The transition metal-containing olefin polymerization catalyst suitablefor the production of the ethylene-based polymer (B) in the presentinvention and satisfying the profitability at the industrial level is,similarly to the ethylene-based polymer(A), appropriately selected fromthe above-described (i) Ziegler catalyst, (ii) metallocene catalyst,(iii) Phillips catalyst and (iv) post-metallocene catalyst and used.

The catalyst used for the production of the ethylene-based polymer (B)in the present invention is more suitably (i) a Ziegler catalyst, (ii) ametallocene catalyst or (iv) a post-metallocene catalyst, still moresuitably (i) a Ziegler catalyst or (ii) a metallocene catalyst. Amongothers, (ii) a metallocene catalyst produces an ethylene-based polymerhaving a narrow molecular weight distribution or a narrowcopolymerization composition distribution as compared with othercatalysts and therefore, is preferred from the standpoint of enhancingthe mechanical properties, transparency, anti-sticking performance, heatseal performance and the like of the polyethylene-based resincomposition or its molded product. Of course, in the case of selecting(iv) a post-metallocene catalyst capable of exerting the sameperformances from the standpoint above, use of the catalyst ispreferred.

Out of the characteristics which the ethylene-based polymer (B) in thepresent invention must satisfy, the particularly importantcharacteristics represented by the condition (B-4) and the condition(B-5). preferably the condition (B-4), the condition (B-5) and thecondition (B-7), are considered to be attributable to a characteristiclong-chain branched structure that is understood to contain a fairlylarge amount of a shortish branch structure sufficiently developed to anextent of enabling branches to intertwine with each other at a levelwhere an elongational strain hardening behavior is observed.

In general, an ethylene-based polymer having a long-chain branch is anethylene-based polymer having a long branching structure (long-chainbranch) in the polyethylene molecule and is contrasted with an ethylenehomopolymer or ethylene.α-olefin copolymer having a normal short-chainbranch (sometimes referred to as straight chain polyethylene). Forproducing such an ethylene-based polymer having a long-chain branch,various methods have been heretofore attempted, and examples thereofinclude a method of directly copolymerizing ethylene and an α-olefin byusing a recent Ziegler catalyst or metallocene catalyst, and a method ofcopolymerizing ethylene and a previously produced macromonomer tointroduce a long-chain branch. Also, an ethylene-based polymer producingusing a catalyst called a Phillips catalyst where the center metal is ahexavalent chromium element, is supposed to contain a small amount of along-chain branched structure. As for the literature specificallydescribing the production of an ethylene-based polymer having along-chain branched structure, the method using a recent Zieglercatalyst is described, for example, in JP-A-60-090203 and JP-10-298234.In these methods, the long-chain branched structure of theethylene-based polymer can be adjusted by appropriately selecting thekind and amount of the organoaluminum compound, the kind of the catalystor the polymerization conditions so as to control the quality and amountof the long-chain branch. As for the production using ametallocene-based catalyst, the method using a complex having a bridgedbiscyclopentadienyl ligand is described, for example, inJP-A-2002-544296 and JP-A-2005-507961; the method using a complex havingan indenyl ligand is described, for example, in JP-A-2-276807,JP-A-2002-308933, JP-A-2004-292772, JP-A-8-311121, JP-A-8-311260 andJP-A-8-48711; the method using a catalyst obtained by combining anon-MAO-modified particle with a complex having a bridged bisindenylligand is described, for example, in JP-A-2004-292772; the method usinga constrained geometry complex catalyst is described, for example, inJP-A-6-306121; and the method using a combination of a benzindenylligand-containing complex with another low-molecular-weightpolyethylene-producing complex is described, for example, inJP-A-2006-2098.

In these methods, the quality and amount of the long-chain branch can becontrolled by appropriately selecting the kind of the complex, thecatalyst preparation conditions or the polymerization conditions. Also,a method of introducing a long-chain branch into a polyethylene chain byusing dienes as a comonomer and copolymerizing it with ethylene isdisclosed, for example, in JP-A-10-512600, and a method of introducing along-chain branch into a polyethylene chain by utilizing a chaintransfer reagent as T-reagent is disclosed, for example, inJP-T-2008-505222. In these methods, the quality and amount of thelong-chain branch can be controlled by controlling the kind or amount ofthe dienes or chain transfer agent or appropriately selecting the kindof the catalyst or the polymerization conditions. Furthermore, a methodwhere a macromonomer is previously produced by using a specificmetallocene-based catalyst and then the macromonomer is copolymerizedwith ethylene, thereby introducing a long-chain branch into apolyethylene chain, is disclosed, for example, in JP-A-7-252311,JP-A-8-502303, International Publication No. 95-11931, JP-T-2001-511215and JP-A-2006-321991. In these methods, the quality and amount of thelong-chain branch can be controlled by appropriately selecting the kindof the complex, the catalyst preparation conditions, the polymerizationconditions, or the amount or molecular weight of the macromonomer. Theindex indicative of such an ethylene-based polymer having a long-chainbranch is generally expressed by various measurement techniques and thelike, for example, by the melt flow rate ratio (MFR ratio; see, forexample, Japanese Patent 2,571,280), the melt tension (MT; see, forexample. Japanese Patent 3,425,719), the presence or absence of risingof elongational viscosity (strain hardening) (see, for example, JapanesePatent 4,190,638), and the activation energy (see, for example,JP-A-7-062031). The resin that is commercially available in practiceincludes, for example, trade name: AFFINITY (registered trademark)FM1570 (produced by Dow Chemical), and trade name: Excellen GMH(registered trademark) (produced by Sumitomo Chemical Co., Ltd.).

However, not all of ethylene-based polymers having a long-chain branchedstructure produce by these methods are suited for the ethylene-basedpolymer (B) as a constituent component of the polyethylene-based resincomposition of the present invention. The present inventors have foundthat selection of the specific ethylene-based polymer (B) leads togreatly different results in the molding characteristics, mechanicalstrength and transparency of the polyethylene-based composition or amolded product of the composition, and in addition to the selection of along-chain branched structure suitable for the present invention, onlywhen an ethylene-based polymer (B) of which MFR, density and molecularweight distribution conditions are suitably designed as described aboveis used as a constituent component of the polyethylene-basedcomposition, the present invention has been accomplished.

The ethylene-based polymer having a long-chain branched structure, whichcan be produced by the conventional technique, includes, as describedabove, a polymer produced using a Ziegler catalyst, a polymer producedusing a complex having a bridged biscyclopentadienyl ligand, a polymerproduced using a bridged bisindenyl ligand, a polymer produced using acatalyst obtained by combining a bridged bisindenyl ligand-containingcomplex with a non-MAO-modified particle, a polymer produced using aconstrained geometry complex catalyst, a polymer produced using acombination of a benzindenyl ligand-containing complex with anotherlow-molecular-weight polyethylene-producing complex, a polymer in whicha long-chain branch is introduced into a polyethylene chain by usingdienes as a comonomer and copolymerizing it with ethylene, a polymer inwhich a long-chain branch is introduced into a polyethylene chain byutilizing a chain transfer reagent as T-reagent, and a polymer producedby a method where a macromonomer is previously produced by using aspecific metallocene-based catalyst and then the macromonomer iscopolymerized with ethylene, thereby introducing a long-chain branchinto a polyethylene chain.

However, when the ethylene-based copolymer produced using a Zieglercatalyst is used as the ethylene-based polymer (B) in the presentinvention, the molecular weight distribution or copolymerizationcomposition distribution may be broadened to make the polyethylene-basedresin composition or its molded product be insufficient in the impactstrength or transparency, or the polymer may be heavily sticky due to alarge amount of low crystalline components, and therefore, this is notpreferred. In addition, with the catalyst above, only a small amount ofan elongated long-chain branched structure can be produced, failing insufficiently enhancing the impact strength or transparency. When anethylene-based copolymer produced using a bridged biscyclopentadienylligand-containing complex or a bridged bisindenyl ligand-containingcomplex is used, the molecular weight distribution tends to bebroadened, making the polyethylene-based resin composition or its moldedproduct be insufficient in the impact strength or transparency, or thechain length of the long-chain branch tends to become long, failing insufficiently enhancing the impact resistance or transparency. When anethylene-based copolymer produced using a catalyst obtained by combininga bridged bisindenyl ligand-containing complex with a non-MAO-modifiedparticle is used, the molecular weight distribution tends to be morebroadened than in the case of using an MAO promoter and in turn, thepolyethylene-based resin composition or its molded product may beinsufficient in the impact strength or transparency. For example,Excellen GMH that is a commercial product produced using the catalystabove in practice has a wide molecular weight distribution and anelongated long-chain branch and lacks in the number of branches, as aresult, the effect of improving the moldability may be low or the impactstrength or transparency may not be sufficiently enhanced. When anethylene-based copolymer produced using a constrained geometry complexcatalyst is used, for example, AFFINITY (for example, FM 1570) that is acommercial product produced using the catalyst above in practice has along chain length of the long-chain branch and lacks in the number ofbranches, as a result, the effect of improving the moldability may below or the impact strength or transparency may not be sufficientlyenhanced. As the case now stands, none of these methods are preferred asthe production method of the ethylene-based polymer (B) in the presentinvention.

The ethylene-based copolymer produced using a combination of abenzindenyl ligand-containing complex with another low-molecular-weightpolyethylene-producing complex is thought to have some possibility ofrealizing a long-chain branched structure required of the ethylene-basedpolymer (B) in the present invention, but for the production of along-chain branched structure, the polymerization conditions may belimited to a low hydrogen concentration, the catalyst conditions such asproportion of a complex used or the polymerization conditions must befurther studied so as to avoid broadening of the molecular weight, orstudies on the setting of MFR or density of the ethylene-based polymer(B) or the ethylene-based polymer (A) combined are required.Furthermore, in order to realize a long-chain branched structureappropriate as the ethylene-based polymer (B) in the present inventionby the method of copolymerizing dienes or the method utilizing a chaintransfer reagent, the kind of the dienes, chain transfer agent orpolymerization catalyst used or the polymerization conditions must befurther studied. In addition, it is considered that problems such ascontamination (odor, coloring, deterioration) of the polymer by theresidual diene or residual chain transfer agent must be solved. Also, inorder to realize a long-chain branched structure appropriate as theethylene-based polymer (B) in the present invention by the method ofproducing a macromonomer and copolymerizing it with ethylene to therebyintroduce a long-chain branch into the polyethylene chain, for example,the kind of the polymerization catalyst used, the polymerizationconditions, and the control of molecular weight, density andcopolymerization ratio of the produced macromer must be further studiedand in addition, since a residual macromer remains as alow-molecular-weight polymer in the polymer or in the polyethylene-basedresin composition containing the polymer as one component, the molecularweight distribution or the copolymerization composition distributiontends to be broadened, leaving high possibility that the impact strengthor transparency of the polyethylene-based resin composition or itsmolded product becomes insufficient, which reveals that the polymer isnot preferred enough. For these reasons, the ethylene-based polymer (B)tends to have a longish chain length of the long-chain branch and inturn, the impact strength and transparency may not be sufficientlyenhanced. Also, it is considered that problems such as contamination(odor, coloring, deterioration) of the polymer must be solved.

That is, as a result of intensive studies to attain the object of thepresent invention, with respect to the olefin polymerization catalystcapable of producing a long-chain branched structure suitable as theethylene-based polymer (B) of the present invention, the presentinventors have reached, as an example, a method where a complex having abridged (cyclopentadienyl)(indenyl) ligand or the like that has beendiscovered recently is used as an essential catalyst component (forexample, JP-A-2011-137146 and [V] Production Method of Ethylene-BasedPolymer of the Present Invention in this description); as anotherexample, a method where a complex having a benzindenyl ligand or thelike is used as a catalyst component (for example, JP-A-2006-2098); and,as still another example, a method where a catalyst using a mixture of ametallocene complex, i.e., a complex having a bridged bis(indenyl)ligand, a bridged bis(azulenyl) ligand or a bridgedbis(cyclopentadienyl) ligand, and a borane or borate compound as acompound for producing a cationic metallocene compound together with anorganoaluminum oxy compound, is used.

The olefin polymerization catalyst containing, as an essentialcomponent, a complex having a bridged (cyclopentadienyl)(indenyl) ligandor the like capable of producing a long-chain branched structuresuitable as the ethylene-based polymer (B) of the present inventioncontains the following component (a-1) and component (b) and, ifdesired, further contains the component (c):

component (a-1): a metallocene compound represented by formula (a-1-1),

component (b): a compound capable of reacting with the metallocenecompound of the component (a-1) to produce a cationic metallocenecompound, and

component (c): a microparticle support.

i) Component (a-1)

The component (a-1) is a metallocene compound represented by thefollowing formula (a-1-1):

[in formula (a-1-1), M represents any one transition metal of Ti, Zr andHf; each of X¹ and X² independently represents a hydrogen atom, ahalogen atom, a hydrocarbon group having a carbon number of 1 to 20, ahydrocarbon group containing an oxygen atom or a nitrogen atom andhaving a carbon number of 1 to 20, a hydrocarbon group-substituted aminogroup having a carbon number of 1 to 20, or an alkoxy group having acarbon number of 1 to 20; each of Q¹ and Q² independently represents acarbon atom, a silicon atom or a germanium atom; each R¹ independentlyrepresents a hydrogen atom or a hydrocarbon group having a carbon numberof 1 to 10 and at least two members out of four R¹ may combine to form aring together with Q¹ and Q²; m is 0 or 1 and when m is 0, Q¹ is bondeddirectly to the conjugated 5-membered ring including R² and R³; each R²independently represents a hydrogen atom, a halogen atom, a hydrocarbongroup having a carbon number of 1 to 20, a silicon-containinghydrocarbon group containing from 1 to 6 silicons and having a carbonnumber of 1 to 18, a halogen-containing hydrocarbon group having acarbon number of 1 to 20, a hydrocarbon group containing an oxygen atomand having a carbon number of 1 to 20, or a hydrocarbongroup-substituted silyl group having a carbon number of 1 to 20 and evenwhen the plurality of R² are a hydrocarbon group or the like, unlike R⁴,these R² do not form a ring together with the carbon atoms to which R²are bonded; R³ represents a saturated or unsaturated divalenthydrocarbon group having a carbon number of 4 or 5 for forming acondensed ring with the 5-membered ring to which R³ is bonded; R⁴ is anatom or a group bonded to a carbon atom of R³ and each independentlyrepresents a hydrogen atom, a halogen atom, a hydrocarbon group having acarbon number of 1 to 20, a silicon-containing hydrocarbon groupcontaining from 1 to 6 silicons and having a carbon number of 1 to 18, ahalogen-containing hydrocarbon group having a carbon number of 1 to 20,or a hydrocarbon group-substituted silyl group having a carbon number of1 to 20; n represents an integer of 0 to 10 and when n is 2 or more, atleast two R⁴ may form a ring together with the carbon atoms to which R⁴are bonded; and each R⁵ independently represents a hydrogen atom, ahalogen atom, a hydrocarbon group having a carbon number of 1 to 20, asilicon-containing hydrocarbon group containing from 1 to 6 silicons andhaving a carbon number of 1 to 18, a halogen atom-containing hydrocarbongroup having a carbon number of 1 to 20, a hydrocarbon group containingan oxygen atom and having a carbon number of 1 to 20, or a hydrocarbongroup-substituted silyl group having a carbon number of 1 to 20 and evenwhen the plurality of R⁵ are a hydrocarbon group or the like, unlike R⁴,these R⁵ do not form a ring together with the carbon atoms to which R⁵are bonded].

In formula (a-1-1), M of the metallocene compound represents Ti, Zr orHf. M is preferably Zr or Hf and from the standpoint that thepolymerization activity is high, M is more preferably Zr. In the presentinvention, this preference order of center metal species applies in alldescriptions of metallocene complexes below.

Each of X¹ and X² independently includes, for example, a hydrogen atom,a chlorine atom, a bromine atom, an iodine atom, a methyl group, anethyl group, an n-propyl group, an i-propyl group, an n-butyl group, ani-butyl group, a tert-butyl group, an n-pentyl group, a neopentyl group,a cyclopentyl group, an n-hexyl group, a cyclohexyl group, a phenylgroup, a benzyl group, a methoxymethyl group, an ethoxymethyl group, ann-propoxymethyl group, an i-propoxymethyl group, an n-butoxymethylgroup, an i-butoxymethyl group, a tert-butoxymethyl group, amethoxyethyl group, an ethoxyethyl group, an acetyl group, a 1-oxopropylgroup, a 1-oxo-n-butyl group, a 2-methyl-1-oxopropyl group, a2,2-dimethyl-1-oxo-propyl group, a phenylacetyl group, a diphenylacetylgroup, a benzoyl group, a 2-methoxyphenyl group, a 3-methoxyphenylgroup, a 4-methoxyphenyl group, a 2-furyl group, a 2-tetrahydrofurylgroup, a dimethylaminomethyl group, a diethylaminomethyl group, adi-i-propylaminomethyl group, a bis(dimethylamino)methyl group, abis(di-i-propylamino)methyl group, a (dimethylamino)(phenyl)methylgroup, a methylimino group, an ethylimino group, a 1-(methylimino)ethylgroup, a 1-(phenylimino)ethyl group, a 1-[(phenylmethyl)imino]ethylgroup, an ethoxy group, an n-propoxy group, an i-propoxy group, ann-butoxy group, an i-butoxy group, a tert-butoxy group, a phenoxy group,a dimethylamino group, a diethylamino group, a di-n-propylamino group, adi-i-propylamino group, a di-n-butylamino group, a di-i-butylaminogroup, a di-tert-butylamino group, and a diphenylamino group.

Specific preferred examples of X¹ and X² include a chlorine atom, abromine atom, a methyl group, an n-butyl group, an i-butyl group, amethoxy group, an ethoxy group, an i-propoxy group, an n-butoxy group, aphenoxy group, a dimethylamino group, and a di-i-propylamino group.Among these specific examples, a chlorine atom, a methyl group and adimethylamino group are more preferred.

Each of Q¹ and Q² independently represents a carbon atom, a silicon atomor a germanium atom and is preferably a carbon atom or a silicon atom.

Each R¹ independently includes, for example, a hydrogen atom, a methylgroup, an ethyl group, an n-propyl group, an i-propyl group, an n-butylgroup, an i-butyl group, a tert-butyl group, an n-pentyl group, aneopentyl group, a cyclopentyl group, an n-hexyl group, a cyclohexylgroup, and a phenyl group. In the case where R¹ forms a ring togetherwith Q¹ and Q², examples include a cyclobutylidene group, acyclopentylidene group, a cyclohexylidene group, a silacyclobutyl group,a silacyclopentyl group, and a silacyclohexyl group.

When Q¹ or/and Q² are a carbon atom, specific preferred examples of R¹include a hydrogen atom, a methyl group, an ethyl group, a phenyl groupand a cyclobutylidene group, and when Q¹ or/and Q² are a silicon atom,specific preferred examples include a methyl group, an ethyl group, aphenyl group and a silacyclobutyl group.

Each R² independently includes, for example, a hydrogen atom, a chlorineatom, a bromine atom, an iodine atom, a methyl group, an ethyl group, ann-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, atert-butyl group, an n-pentyl group, a neopentyl group, a cyclopentylgroup, an n-hexyl group, a cyclohexyl group, a phenyl group, a benzylgroup, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenylgroup, a 3,5-dimethylphenyl group, a 4-tert-butylphenyl group, a3,5-di-tert-butylphenyl group, a bis(trimethylsilyl)methyl group, abis(tert-butyldimethylsilyl)methyl group, a bromomethyl group, achloromethyl group, a 2-chloroethyl group, a 2-bromoethyl group, a2-bromopropyl group, a 3-bromopropyl group, a 2-bromocyclopentyl group,a 2,3-dibromocyclopentyl group, a 2-bromo-3-iodocyclopentyl group, a2,3-dibromocyclohexyl group, a 2-chloro-3-iodocyclohexyl group, a2-chlorophenyl group, a 4-chlorophenyl group, a2,3,4,5,6-pentafluorophenyl group, a 4-trifluoromethylphenyl group, afuryl group, a tetrahydrofuryl group, a 2-methylfuryl group, atrimethylsilyl group, a tri-tert-butylsilyl group, adi-tert-butylmethylsilyl group, a tert-butyldimethylsilyl group, atriphenylsilyl group, a diphenylmethylsilyl group, and aphenyldimethylsilyl group.

Out of two R², at least one is preferably a hydrocarbon group having acarbon number of 1 to 20, a silicon-containing hydrocarbon groupcontaining from 1 to 6 silicons and having a carbon number of 1 to 18, ahalogen-containing hydrocarbon group having a carbon number of 1 to 20,a hydrocarbon group containing an oxygen atom and having a carbon numberof 1 to 20, or a hydrocarbon group-substituted silyl group having acarbon number of 1 to 20, because the polymerization activity becomeshigh in particular. Also, R² on the 2-position is preferably a hydrogenatom, because the characteristics of the long-chain branched structureare particularly improved and in turn, the moldability is excellent.

Specific preferred examples of R², each independently, include ahydrogen atom, a methyl group, an ethyl group, an n-propyl group, ani-propyl group, an n-butyl group, a tert-butyl group, an n-pentyl group,an n-hexyl group, a cyclohexyl group, a phenyl group, a 2-methylfurylgroup, and a trimethylsilyl group.

Among these specific examples, a hydrogen atom, a methyl group, ann-butyl group, a tert-butyl group, a phenyl group and a trimethylsilylgroup are more preferred, and a hydrogen atom, a methyl group and aphenyl group are still more preferred.

Specific examples of the condensed cyclopentadienyl structure formed byR³ and a cyclopentadienyl moiety to which R³ is bonded, include thefollowing partial structures (I) to (VI).

Among these specific examples, (I), (III) and (VI) are preferred. Also,R⁴ may be substituted on these partial structures (I) to (VI).

The substituent R⁴ includes, in addition to a hydrogen atom, forexample, a chlorine atom, a bromine atom, an iodine atom, a methylgroup, an ethyl group, an n-propyl group, an i-propyl group, an n-butylgroup, an i-butyl group, a tert-butyl group, an n-pentyl group, aneopentyl group, a cyclopentyl group, an n-hexyl group, a cyclohexylgroup, a phenyl group, a benzyl group, a 2-methylphenyl group, a3-methylphenyl group, a 4-methylphenyl group, a 4-tert-butylphenylgroup, a 3,5-dimethylphenyl group, a 3,5-di-tert-butylphenyl group, anaphthyl group, an anthracenyl group, a bis(trimethylsilyl)methyl group,a bis(tert-butyldimethylsilyl)methyl group, a bromomethyl group, achloromethyl group, a 2-chloroethyl group, a 2-bromoethyl group, a2-bromopropyl group, a 3-bromopropyl group, a 2-bromocyclopentyl group,a 2,3-dibromocyclopentyl group, a 2-bromo-3-iodocyclopentyl group, a2,3-dibromocyclohexyl group, a 2-chloro-3-iodocyclohexyl group, a2-chlorophenyl group, a 4-chlorophenyl group, a2,3,4,5,6-pentafluorophenyl group, a 2,6-dichloro-4-trimethylsilylphenylgroup, a trimethylsilyl group, a tri-tert-butylsilyl group, adi-tert-butylmethylsilyl group, a tert-butyldimethylsilyl group, atriphenylsilyl group, a diphenylmethylsilyl group, and aphenyldimethylsilyl group.

In the case where two or more R⁴ form a ring together with the carbonatoms to which R⁴ are bonded, examples include a benz[e]indenyl group, abenz[f]indenyl group, a 6,7-dihydroindacenyl group, a5,5,7,7-tetramethyl-6,7-dihydroindacenyl group, a5,6,7,8-tetrahydro-benz[f]indenyl group, and a5,6,7,8-tetrahydro-5,5,8,8-tetramethyl-benz[f]indenyl group.

Specific preferred examples of R⁴ include a methyl group, an ethylgroup, an n-propyl group, an i-propyl group, an n-butyl group, atert-butyl group, an n-pentyl group, an n-hexyl group, a cyclohexylgroup, a phenyl group, a naphthyl group, and a trimethylsilyl group.

Each R⁵ independently includes, for example, a hydrogen atom, a chlorineatom, a bromine atom, an iodine atom, a methyl group, an ethyl group, ann-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, atert-butyl group, an n-pentyl group, a neopentyl group, a cyclopentylgroup, an n-hexyl group, a cyclohexyl group, a phenyl group, a benzylgroup, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenylgroup, a 3,5-dimethylphenyl group, a 4-tert-butylphenyl group, a3,5-di-tert-butylphenyl group, a bis(trimethylsilyl)methyl group, abis(tert-butyldimethylsilyl)methyl group, a bromomethyl group, achloromethyl group, a 2-chloroethyl group, a 2-bromoethyl group, a2-bromopropyl group, a 3-bromopropyl group, a 2-bromocyclopentyl group,a 2,3-dibromocyclopentyl group, a 2-bromo-3-iodocyclopentyl group, a2,3-dibromocyclohexyl group, a 2-chloro-3-iodocyclohexyl group, a2-chlorophenyl group, a 4-chlorophenyl group, a2,3,4,5,6-pentafluorophenyl group, a 4-trifluoromethylphenyl group, afuryl group, a tetrahydrofuryl group, a 2-methylfuryl group, atrimethylsilyl group, a tri-tert-butylsilyl group, adi-tert-butylmethylsilyl group, a tert-butyldimethylsilyl group, atriphenylsilyl group, a diphenylmethylsilyl group, and aphenyldimethylsilyl group.

Out of four R⁵, at least one is preferably a hydrocarbon group having acarbon number of 1 to 20, a silicon-containing hydrocarbon groupcontaining from 1 to 6 silicons and having a carbon number of 1 to 18, ahalogen-containing hydrocarbon group having a carbon number of 1 to 20,a hydrocarbon group containing an oxygen atom and having a carbon numberof 1 to 20, or a hydrocarbon group-substituted silyl group having acarbon number of 1 to 20, because the polymerization activity isparticularly increased. Also, R⁵ on the 2-position and 5-position arepreferably a hydrogen atom, because the characteristics of thelong-chain branched structure are particularly improved and in turn, themoldability is excellent.

Specific preferred examples of R⁵ include a hydrogen atom, a methylgroup, an ethyl group, an n-propyl group, an i-propyl group, an n-butylgroup, a tert-butyl group, an n-pentyl group, an n-hexyl group, acyclohexyl group, a phenyl group, a 2-methylfuryl group, and atrimethylsilyl group.

Among these specific examples, a hydrogen atom, a methyl group, ann-butyl group, a tert-butyl group, a phenyl group and a trimethylsilylgroup are more preferred, and a hydrogen atom, a methyl group, atert-butyl group and a phenyl group are still more preferred.

In formula (a-1-i), m is 0 or 1 and when m is 0, Q¹ is bonded directlyto the conjugated 5-membered ring including R² and R³. Furthermore, nrepresents an integer of 0 to 10 and when n is 2 or more, at least twoR⁴ may form a ring together with the carbon atoms to which R⁴ arebonded.

The metallocene compound of the component (a-1) is preferably a compoundrepresented by the following formula (a-1-2), more preferably a compoundrepresented by the following formula (a-1-3):

In the metallocene compounds represented by formulae (a-1-2) and(a-1-3), for X¹, X², Q, R¹, R², R⁴ and R⁵, the same structures as theatoms and groups described in the metallocene compound represented byformula (a-1-1) may be selected.

Specific examples of the metallocene compound of the component (a-1) areshown in Tables a-1 to a-4 below, but the present invention is notlimited thereto. In Tables a-1 to a-4, Cp stands for a cyclopentadienylgroup, Ind stands for an indenyl group, Me stands for a methyl group, Phstands for a phenyl group, Et stands for an ethyl group, nPr stands foran n-propyl group, nBu stands for an n-butyl group, nC5 stands for ann-pentyl group, nC6 stands for an n-hexyl group, Bz stands for a benzylgroup, and Azu stands or an azulenyl group.

TABLE a-1 (i) Bridged Cp(Ind)Zr Type

Cp Ind No. Q Substituent Substituent X  1a Me2Si — — Cl  2a Me2Si — — Me 3a Me2Si — — Ph  4a Me2C — — Cl  5a silacyclobutyl — — Cl  6asilacyclopentyl — — Cl  7a silacyclohexyl — — Cl  8a cyclobutylidene — —Cl  9a cyclopentylidene — — Cl 10a cyclohexylidene — — Cl

TABLE a-2 (ii) Bridged Cp(3-substituted Ind)Zr Type

Cp Ind No. Q Substituent Substituent X 11a Me2Si — 3-Me Cl 12a Me2Si —3-Me Me 13a Me2C — 3-Me Cl 14a Me2Si — 3-Et Cl 15a Me2C — 3-Et Cl 16aMe2Si — 3-nPr Cl 17a Me2C — 3-nPr Cl 18a Me2Si — 3-iPr Cl 19a Me2C —3-iPr Cl 20a Me2Si — 3-nBu Cl 21a Me2C — 3-nBu Cl 22a Me2Si — 3-tBu Cl23a cyclobutylidene — 3-tBu Cl 24a Me2Si — 3-tBu Me 25a Me2C — 3-tBu Cl26a Me2Si — 3-nC5 Cl 27a Me2Si — 3-nC6 Cl 28a Me2Si — 3-cycC6 Cl 29aMe2Si — 3-Ph Cl 30a Me2Si — 3-Bz Cl 31a Me2Si — 3-tolyl Cl 32a Me2Si —3-TMS Cl 33a Me2Si — 3-ClPh Cl 34a Me2Si — 3-FPh Cl 35a Me2Si — 4-Me Cl36a Me2Si — 5-Me Cl 37a Me2Si — 6-Me Cl 38a Me2Si — 3,4-Me2 Cl 39a Me2Si— 3-tBu-4-Me Cl 40a Me2Si — 4-Ph Cl

TABLE a-3 (ii) Bridged Cb(3-Substituted Ind)Zr Type (continued) No. Q CpSubstituent Ind Substituent X 41a Me2Ge — — Cl 42a Me2Ge — 3-Me Cl 43aMe2Ge — 3-Et Cl 44a Me2Ge — 3-iPr Cl 45a Me2Ge — 3-nBu Cl 46a Me2Ge —3-tBu Cl 47a Et2Si — — Cl 48a Et2Si — 3-Me Cl 49a Et2Si — 3-Et Cl 50aEt2Si — 3-iPr Cl 51a Et2Si — 3-nBu Cl 52a Et2Si — 3-tBu Cl 53a nBu2Si —— Cl 54a nBu2Si — 3-Me Cl 55a nBu2Si — 3-Et Cl 56a nEu2Si — 3-iPr Cl 57anBu2Si — 3-nBu Cl 58a nBu2Si — 3-tBu Cl 59a Ph2Si — — Cl 60a Ph2C — — Cl61a Ph2Si — 3-Me Cl 62a Ph2Si — 3-Et Cl 63a Ph2Si — 3-iPr Cl 64a Ph2Si —3-nBu Cl 65a Ph2Si — 3-tBu Cl 66a Me2Si — benz[e] Cl 67a Me2Si — dibenzoCl 68a Me2Si — azulenyl Cl 69a Me2Si — 4-Me-Azu Cl 70a Me2Si — 4-Ph-AzuCl 71a Me2Si — 5,6-Me2 Cl 72a Me2Si — benz[f] Cl 73a Me2Si —6,7-dihydroindacenyl Cl 74a Me2Si — 5,5,7,7-Me4-6,7-dihydroindacenyl Cl75a Me2Si — 5,6,7,8-H4-benz[f] Cl 76a Me2Si —5,6,7,8-H4-5,5,8,8-Me4-benz[f] Cl

TABLE a-4 (iv) Bridged (4-Substituted Cp)(3-Substituted Ind)Zr Type

No. Q Cp Substituent Ind Substituent X 77a Me2Si 4-tBu 3-Me Cl 78a Me2Si4-tBu 3-tBu Cl 79a Me2Si 4-tBu 3-tBu Me 80a Me2Si 4-tBu 2-Me Cl 81aMe2Si 4-tBu 2-Me-4Ph Cl 82a Me2C 2-Me 3-tBu Cl 83a Me2Si 4-tBu — Cl 84aMe2Si 2,3-Me2 3-tBu Cl 85a Me2Si 2,3,4-Me3 — Cl 86a Me2Si 2,3,4,5-Me4 —Cl 87a Me2Si 4-tBu — Me 88a Me2Si 4-tBu 4,5,6,7-H4 Cl 89a Me2Si 4-tBuAzu Cl 90a Me2Si 4-tBu 2-(2-Me-Furyl) Cl 91a Me2Si 2-(2-Me-Furyl) 3-MeCl 92a Me2Si 4-TMS — Cl 93a Me2Si 4-(2-Br—Et) — Cl

The metallocene compound also includes, for example, compounds wherezirconium of the compounds above is replaced by titanium or hafnium.

Furthermore, in using these metallocene compounds as the component(a-1), two or more thereof may be also used.

Among specific compounds exemplified above, preferred metallocenecompounds as the component (a-1) include the followings.

That is, preferred examples includedimethylsilylene-(cyclopentadienyl)(indenyl)zirconium dichloride,dimethylsilylene(cyclopentadienyl)(indenyl)zirconium dimethyl,isopropylidene(cyclopentadienyl)(indenyl)zirconium dichloride,dimethylsilylene(cyclopentadienyl)(3-methylindenyl)zirconium dichloride,dimethylsilylene(cyclopentadienyl)(3-methylindenyl)zirconium dimethyl,isopropylidene(cyclopentadienyl)(3-methylindenyl)zirconium dichloride,dimethylsilylene(cyclopentadienyl)(3-n-butylindenyl)zirconiumdichloride, dimethylsilylene(cyclopentadienyl)(3-phenylindenyl)zirconiumdichloride, isopropylidene(cyclopentadienyl)(3-n-butylindenyl)zirconiumdichloride,dimethylsilylene(cyclopentadienyl)(3-tert-butylindenyl)zirconiumdichloride,dimethylsilylene(cyclopentadienyl)(3-tert-butylindenyl)zirconiumdimethyl, dimethylsilylene(cyclopentadienyl)(4-phenylindenyl)zirconiumdichloride, dimethylsilylene(cyclopentadienyl)(benz[e]indenyl)zirconiumdichloride,isopropylidene(cyclopentadienyl)(3-tert-butylindenyl)zirconiumdichloride,cyclobutylidene(cyclopentadienyl)(3-tert-butylindenyl)zirconiumdichloride, dimethylgermirene(cyclopentadienyl)(indenyl)zirconiumdichloride, diphenylsilylene-(cyclopentadienyl)(indenyl)zirconiumdichloride, diphenylmethylene(cyclopentadienyl)(indenyl)zirconiumdichloride, dimethylsilylene(cyclopentadienyl)(azulenyl)zirconiumdichloride,dimethylsilylene(4-tert-butylcyclopentadienyl)(3-methylindenyl)zirconiumdichloride,dimethylsilylene(4-tert-butylcyclopentadienyl)(3-tert-butylindenyl)zirconiumdichloride,dimethylsilylene(4-tert-butylcyclopentadienyl)(3-tert-butylindenyl)zirconiumdimethyl,dimethylsilylene(4-tert-butylcyclopentadienyl)(4-phenylindenyl)zirconiumdichloride,dimethylsilylene(4-tert-butylcyclopentadienyl)(indenyl)zirconiumdichloride,dimethylsilylene(4-tert-butylcyclopentadienyl)(indenyl)zirconiumdichloride,dimethylsilylene(4-tert-butylcyclopentadienyl)(indenyl)zirconiumdimethyl,dimethylsilylene(4-tert-butylcyclopentadienyl)(4,5,6,7-tetrahydroindenyl)zirconiumdichloride,dimethylsilylene(4-tert-butylcyclopentadienyl)(azulenyl)zirconiumdichloride, and compounds where zirconium of the compounds above isreplaced by titanium or hafnium.

Among specific examples exemplified above, more preferred examples ofthe metallocene compound as the component (a-1) include the followings:dimethylsilylene(cyclopentadienyl)(indenyl)zirconium dichloride,isopropylidene(cyclopentadienyl)(indenyl)zirconium dichloride,dimethylsilylene(cyclopentadienyl)(3-methylindenyl)zirconium dichloride,dimethylsilylene(cyclopentadienyl)(3-phenylindenyl)zirconium dichloride,dimethylsilylene(cyclopentadienyl)(4-phenylindenyl)zirconium dichloride,dimethylsilylene(cyclopentadienyl)(benz[e]indenyl)zirconium dichloride,isopropylidene(cyclopentadienyl)(3-methylindenyl)zirconium dichloride,dimethylsilylene(cyclopentadienyl)(3-tert-butylindenyl)zirconiumdichloride,isopropylidene(cyclopentadienyl)(3-tert-butylindenyl)zirconiumdichloride, dimethylgremirene(cyclopentadienyl)(indenyl)zirconiumdichloride,cyclobutylidene(cyclopentadienyl)(3-tert-butylindenyl)zirconiumdichloride, dimethylsilylene(cyclopentadienyl)(indenyl)hafniumdichloride, dimethylsilylene(cyclopentadienyl)(3-methylindenyl)hafniumdichloride,dimethylsilylene(cyclopentadienyl)(3-tert-butylindenyl)hafniumdichloride,dimethylsilylene(4-tert-butylcyclopentadienyl)(indenyl)zirconiumdichloride,dimethylsilylene(4-tert-butylcyclopentadienyl)indenyl)zirconiumdichloride, anddimethylsilylene(4-tert-butylcyclopentadienyl)indenyl)zirconiumdimethyl.

ii) Component (b)

The olefin polymerization catalyst recited as an example of the olefinpolymerization catalyst containing, as an essential component, a complexhaving a bridged (cyclopentadienyl)(indenyl) ligand or the like capableof producing a long-chain branched structure suitable as theethylene-based polymer (B) of the present invention contains, inaddition to the component (a-1), a compound capable of reacting with themetallocene compound of the component (a-1) (component (a-1);hereinafter, sometimes simply referred to as “a”) to produce a cationicmetallocene compound (component (b); hereinafter, sometimes simplyreferred to as “b”).

One of the compound (b) capable of reacting with the metallocenecompound (a) to produce a cationic metallocene compound is anorganoaluminum oxy compound.

The organoaluminum oxy compound has an Al—O—Al bond in the molecule, andthe number of bonds is usually from 1 to 100, preferably from 1 to 50.Such an organoaluminum oxy compound is a product obtained usually byreacting an organoaluminum compound and water.

Incidentally, out of the organoaluminum oxy compounds, the compoundobtained by reacting an alkyl aluminum and water is usually called analuminoxane, and methylaluminoxane (encompasses those substantiallycomposed of methylaluminoxane (MAO)) is particularly suitable as theorganoaluminum oxy compound.

Other specific examples of the compound (b) capable of reacting with themetallocene compound (a) to form a cationic metallocene compound includea borane compound and a borate compound.

Specific examples of the borane compound include triphenylborane,tri(o-tolyl)borane, tri(p-tolyl)borane, tri(m-tolyl)borane,tri(o-fluorophenyl)borane, tris(p-fluorophenyl)borane,tris(m-fluorophenyl)borane, tris(2,5-difluorophenyl)borane,tris(3,5-difluorophenyl)borane, tris(4-trifluoromethylphenyl)borane,tris(3,5-ditrifluoromethylphenyl)borane,tris(2,6-ditrifluoromethylphenyl)borane, tris(pentafluorophenyl)borane,tris(perfluoronaphthyl)borane, tris(perfluorobiphenyl),tris(perfluoroanthryl)borane, and tris(perfluorobinaphthyl)borane.

Also, the borate compound is specifically, as a first example, acompound represented by the following formula (b-1):

[L¹-H]⁺[BR⁶R⁷X⁴X⁵]  formula (b-1)

In formula (b-1), L¹ is a neutral Lewis base, H is a hydrogen atom, and[L¹-H] is a Broensted acid such as ammonium, anilinium and phosphonium.

Examples of the ammonium include a trialkyl-substituted ammonium such astrimethylammonium, triethylammonium, tripropylammonium, tributylammoniumand tri(n-butyl)ammonium, and a dialkylammonium such asdi(n-propyl)ammonium and dicyclohexylammonium.

Examples of the anilinimn include an N,N-dialkyl anilinium such asN,N-dimethylanilinium. N,N-diethylanilinium andN,N-2,4,6-pentamethylanilinium.

Furthermore, the phosphonium includes a triarylphosphonium and atrialkylarylphosphonium, such as triphenylphosphonium,tributylphosphonium, tri(methylphenyl)phosphonium andtri(dimethylphenyl)phosphonium.

In formula (b-1), R^(6b) and R⁷ are, each independently, the same ordifferent aromatic or substituted aromatic hydrocarbon group having acarbon number of 6 to 20, preferably from 6 to 16, and may be connectedto each other by a bridging group. The substituent of the substitutedaromatic hydrocarbon group is preferably an alkyl group typified, forexample, by a methyl group, an ethyl group, a propyl group and anisopropyl group, or a halogen atom such as fluorine, chlorine, bromineand iodine.

Each of X⁴ and X⁵ is independently a hydride group, a halide group, ahydrocarbon group having from 1 to 20 carbon atoms, or a substitutedhydrocarbon group having from 1 to 20 carbon atoms, in which one or morehydrogen atoms are substituted for by a halogen atom.

Specific examples of the compound represented by formula (b-1) includetributylammoniumtetra(pentafluorophenyl)borate,tributylammoniumtetra(2,6-ditrifluoromethylphenyl)borate,tributylammoniumtetra(3,5-ditrifluoromethylphenyl)borate,tributylammoniumtetra(2,6-difluorophenyl)borate,tributylammoniumtetra(perfluoronaphthyl)borate,dimethylaniliniumtetra(pentafluorophenyl)borate,dimethylaniliniumtetra(2,6-ditrifluoromethylphenyl)borate,dimethylaniliniumtetra(3,5-ditrifluoromethylphenyl)borate,dimethylaniliniumtetra(2,6-difluorophenyl)borate,dimethylaniliniumtetra(perfluoronaphthyl)borate,triphenylphosphoniumtetra(pentafluorophenyl)borate,triphenylphosphoniumtetra(2,6-ditrifluoromethylphenyl)borate,triphenylphosphoniumtetra(3,5-ditrifluoromethylphenyl)borate,triphenylphosphoniumtetra(2,6-difluorophenyl)borate,triphenylphosphoniumtetra(perfluoronaphthyl)borate,trimethylammoniumtetra(2,6-ditrifluoromethylphenyl)borate,triethylammoniumtetra(pentafluorophenyl)borate,triethylammoniumtetra(2,6-ditrifluoromethylphenyl)borate,triethylammoniumtetra(perfluoronaphthyl)borate,tripropylammoniumtetra(pentafluorophenyl)borate,tripropylammoniumtetra(2,6-ditrifluoromethylphenyl)borate,tripropylammoniumtetra(perfluoronaphthyl)borate,di(1-propyl)ammoniumtetra(pentafluorophenyl)borate, anddicyclohexylammoniumtetraphenylborate.

Among these, preferred aretributylammoniumtetra(pentafluorophenyl)borate,tributylammoniumtetra(2,6-ditrifluoromethylphenyl)borate,tributylammoniumtetra(3,5-ditrifluoromethylphenyl)borate,tributylammoniumtetra(perfluoronaphthyl)borate,dimethylaniliniumtetra(pentafluorophenyl)borate,dimethylanilinumtetra(2,6-ditrifluoromethylphenyl)borate,dimethylaniliniumtetra(3,5-ditrifluoromethylphenyl)borate anddimethylaniliniumtetra(perfluoronaphthyl)borate.

A second example of the borate compound is represented by the followingformula (b-2):

[L²]⁺[BR⁶R⁷X⁴X⁵]  formula (b-2)

In formula (b-2), L² includes, for example, a carbo-cation, a methylcation, an ethyl cation, a propyl cation, an isopropyl cation, a butylcation, an isobutyl cation, a tert-butyl cation, a pentyl cation, atropinium cation, a benzyl cation, a trityl cation, a sodium cation, anda proton.

R⁶, R⁷, X⁴ and X⁵ have the same definitions as those in formula (b-1).

Specific examples of the compound above include trityltetraphenylborate,trityltetra(o-tolyl)borate, trityltetra(p-tolyl)borate,trityltetra(m-tolyl)borate, trityltetra(o-fluorophenyl)borate,trityltetra(p-fluorophenyl)borate, trityltetra(m-fluorophenyl)borate,trityltetra(3,5-difluorophenyl)borate,trityltetra(pentafluorophenyl)borate,trityltetra(2,6-ditrifluoromethylphenyl)borate,trityltetra(3,5-ditrifluoromethylphenyl)borate,trityltetra(perfluoronaphthyl)borate, tropiniumtetraphenylborate,tropiniumtetra(o-tolyl)borate, tropiniumtetra(p-tolyl)borate,tropiniumtetra(m-tolyl)borate, tropiniumtetra(o-fluorophenyl)borate,tropiniumtetra(p-fluorophenyl)borate,tropiniumtetra(m-fluorophenyl)borate,tropiniumtetra(3,5-difluorophenyl)borate,tropiniumtetra(pentafluorophenyl)borate,tropiniumtetra(2,6-ditrifluoromethylphenyl)borate,tropiniumtetra(3,5-ditrifluoromethylphenyl)borate,tropiniumtetra(perfluoronaphthyl)borate, NaBPh₄, NaB(o-CH₃-Ph)₄,NaB(p-CH₃-Ph)₄, NaB(m-CH₃-Ph)₄, NaB(o-F-Ph)₄, NaB(p-F-Ph)₄,NaB(m-F-Ph)₄, NaB(3,5-F-Ph)₄, NaB(C₆F₅)₄, NaB(2,6-(CF₃)₂-Ph)₄,NaB(3,5-(CF₃)₂-Ph)₄, NaB(C₁₀F₇)₄, H⁺BPh₄.2-diethyl ether,H⁺B(3,5-F₂-Ph)₄.2-diethyl ether, H⁺B(C₆F₅)₄ ⁻.2-diethyl ether,H⁺B(2,6-(CF₃)₂-Ph)₄.2-diethyl ether, H⁺B(3,5-(CF₃)₂-Ph)₄.2-diethylether, and H⁺B(C₁₀H₇)₄.2-diethyl ether.

Among these, preferred are trityltetra(pentafluorophenyl)borate,trityltetra(2,6-ditrifluoromethylphenyl)borate,trityltetra(3,5-ditrifluoromethylphenyl)borate,trityltetra(perfluoronaphthyl)borate,tropiniumtetra(pentafluorophenyl)borate,tropiniumtetra(2,6-ditrifluoromethylphenyl)borate,tropiniumtetra(3,5-ditrifluoromethylphenyl)borate,tropiniumtetra(perfluoronaphthyl)borate, NaB(C₆F₅)₄,NaB(2,6-(CF₃)₂-Ph)₄, NaB(3,5-(CF₃)₂-Ph)₄, NaB(C₁₀F₇)₄, H⁺B(C₆F₅)₄⁻.2-diethyl ether, H⁺B(2,6-(CF₃)₂-Ph)₄.2-diethyl ether,H⁺B(3,5-(CF₃)₂-Ph)₄.2-diethyl ether and H⁺B(C₁₀H₇)₄.2-diethyl ether.

Among these, more preferred are trityltetra(pentafluorophenyl)borate,trityltetra(2,6-ditrifluoromethylphenyl)borate,tropiniumtetra(pentafluorophenyl)borate,tropiniumtetra(2,6-ditrifluoromethylphenyl)borate, NaB(C₆F₅)₄,NaB(2,6-(CF₃)₂-Ph)₄, H⁺B(C₆F₅)₄ ⁻.2-diethyl ether,H⁺B(2,6-(CF₃)₂-Ph)₄.2-diethyl ether, H⁺B(3,5-(CF₃)₂-Ph)₄.2-diethyl etherand H⁺B(C₁₀H₇)₄.2-diethyl ether.

When a borane compound or a borate compound is used as the catalystcomponent (b), the polymerization activity or copolymerizabilityincreases and therefore, productivity of an ethylene-based polymerhaving a long-chain branch is enhanced.

Other specific examples of the compound (b) capable of reacting with ametallocene compound (a) to produce a cationic metallocene compoundinclude a clay mineral a layered silicate compound, and a chemicallytreated solid oxide.

In addition, a mixture of the above-described organoaluminum oxycompound and the above-described borane compound or borate compound maybe also used as the component (b), and in order to more enhance thelong-chain branched structure required of the ethylene-based polymer (B)in the present invention, it is preferred to use the borane compound orborate compound in combination with the organoaluminum oxy compound.Furthermore, as for the borane compound or borate compound, two or morecompounds may be mixed and used.

iii) Component (c)

The olefin polymerization catalyst recited as an example of the olefinpolymerization catalyst containing, as an essential component, a complexhaving a bridged (cyclopentadienyl)(indenyl) ligand or the like capableof producing a long-chain branched structure suitable as theethylene-based polymer (B) of the present invention preferably containsa microparticle support (component (c); hereinafter, sometimes simplyreferred to as “c”).

The microparticle support as the component (c) includes an inorganicsupport, a particulate polymer support, and a mixture thereof. As theinorganic support, a metal, a metallic oxide, a metallic chloride, ametallic carbonate, a carbonaceous substance, or a mixture thereof canbe used.

Preferred examples of the metal that can be used for the inorganicsupport include iron, aluminum, and nickel.

The metallic oxide includes a single oxide or a composite oxide ofelements belonging to Groups 1 to 14 of the periodic table, and examplesthereof include various natural or synthetic, single or composite oxidessuch as SiO₂, Al₂O₃, MgO, CaO, B₂O₃, TiO₂, ZrO₂, Fe₂O₃, Al₂O₃.MgO,Al₂O₃.CaO, Al₂O₃.SiO₂, Al₂O₃.MgO.CaO, Al₂O₃.MgO.SiO₂, Al₂O₃.CuO,Al₂O₃.Fe₂O₃, Al₂O₃.NiO and SiO₂.MgO.

Incidentally, these formulae are not a molecular formula but indicateonly a composition, and the structure and component ratio of thecomposite oxide for use in the present invention are not particularlylimited.

Also, the metallic oxide for use in the present invention may haveabsorbed a small amount of water or may contain a small amount ofimpurities.

As the metallic chloride, for example, a chloride of an alkali metal oran alkaline earth metal is preferred, and specifically, MgCl₂, CaCl₂ andthe like are suited in particular.

As the metallic carbonate, a carbonate of an alkali metal or an alkalineearth metal is preferred, and specific examples thereof includemagnesium carbonate, calcium carbonate, and barium carbonate.

The carbonaceous substance includes, for example, carbon black andactivated carbon.

All of these inorganic supports can be suitably used in the presentinvention, but among others, use of a metallic oxide, silica, alumina orthe like is preferred.

A specific example of the olefin polymerization catalyst containing, asan essential component, a benzindenyl ligand or the like capable ofproducing a long-chain branched structure suitable as the ethylene-basedpolymer (B) of the present invention is an olefin polymerizationcatalyst comprising the following component (a-2), the component (b),and the preferred component (c).

iv) Component (a-2)

The component (a-2) is a metallocene compound having one or more,preferably two or more, more preferably three, benzindenyl ligands arerepresented by the following formula (a-2-1):

Here, each of the substituents R⁸ to R¹³ is independently a hydrocarbongroup having a carbon number of 1 to 30, or a trialkyl silicon grouphaving a hydrocarbon substituent with a carbon number of 1 to 30.Specific examples of the hydrocarbon group include an alkyl group suchas methyl group, ethyl group, propyl group, butyl group, pentyl group,hexyl group and cyclohexyl group; an alkenyl group such as vinyl groupand allyl group; an aryl group such as phenyl group, dimethylphenylgroup, diethylphenyl group, dipropylphenyl group, dibutylphenyl group,trimethylphenyl group, triethylphenyl group, tripropylphenyl group,tributylphenyl group, biphenyl group, naphthyl group and anthryl group:an arylalkyl group such as trityl group, phenethyl group, benzhydrylgroup, phenylpropyl group, phenylbutyl group and neophyl group; and anarylalkenyl group such as styryl group. These groups may have a branch.Also, out of the substituents R⁸ to R¹³, adjacent two substituents mayform a ring together with the carbon atoms to which the substituents arebonded. In addition, when the component (a-2) has three cyclopentadienylskeleton-containing ligands including the benzindenyl ligand, ametallocene complex where two or more members of those ligands arebridged, for example, by the same ethylene bridging group ordimethylsilylene groups as the bridging group composed of Q¹, Q² and R¹defined in formula (a-1-1), such as hydrocarbon group, silylene groupand substituted silylene group, is also effective. Incidentally, thecenter transition metal and the group (auxiliary ligand) except for acyclopentadienyl skeleton-containing ligand bonded to the centertransition metal are the same as those of M, X¹ and X² defined informula (a-1-1), such as hydrocarbon group, alkoxyl group, halogen atomand hydrogen atom.

Specific examples of the component (a-2) where, for example, the centertransition metal is Zr, are shown in Tables a-5 and a-6 below. In Tablesa-5 and a-6, Cp stands for a cyclopentadienyl group, Ind stands for anindenyl group, Bzind stands for a benzindenyl group, Dbi stands for adibenzindenyl group, Me stands for a methyl group, and Bu stands for abutyl group.

TABLE a-5 ABCDZr No. A B C D  95a BzInd BzInd Cl Cl  96a BzInd BzInd BrBr  97a BzInd BzInd Me Me  98a Dbi Dbi Cl Cl  99a Dbi Dbi Br Br 100a DbiDbi Me Me 101a BzInd BzInd BzInd H 102a Dbi Dbi Dbi H 103a BzInd BzIndCp H 104a BzInd BzInd 1,3-Me2-Cp H 105a BzInd BzInd 1-Bu-3-Me-Cp H 106aBzInd BzInd Ind H 107a BzInd Ind Ind H 108a Dbi Dbi Cp H 109a Dbi Cp CpH 110a Dbi Dbi Ind H 111a Dbi Ind Ind H 112a BzInd BzInd Dbi H 113aBzInd Dbi Dbi H 114a BzInd Dbi Cp H 115a BzInd Dbi Ind H

TABLE a-6

No. A1 A2 A3 A4 A5 116a Et Ind Ind BzInd H 117a Et Ind Ind Dbi H 118aMe2Si Cp Cp BzInd H 119a Me2Si Cp Cp Dbi H 120a Me2Si Cp Ind Dbi H 121aEt BzInd BzInd Cp H 122a Et BzInd BzInd Ind H

Specific preferred examples of the component (a-2) are Bzind₃ZrH,Dbi₃ZrH, Bzind₂CpZrH, Bzind₂(1,3-Me₂Cp)ZrH, Bzind₂(1-Bu-3-MeCp)ZrH,Bzind₂IndZrH, BzindInd₂ZrH, Dbi₂CpZrH, DbiCp₂ZrH, Dbi₂IndZrH,DbiInd₂ZrH, Bzind₂DbiZrH, BzindDbi₂ZrH, BzindDbiCpZrH, BzindDbiIndZrH,Et(Ind)₂BzindZrH, Et(Ind)₂DbiZrH, Me₂SiCp₂BzindZrH, Me₂SiCp₂DbiZrH,Me₂Si(Cp)(Ind)DbiZrH, Et(Bzind)₂CpZrH and Et(Bzind)₂IndZrH, and morepreferred specific examples are Bzind₃ZrH, Dbi₃ZrH, Bzind₂CpZrH,Bzind₂(1,3-MeCp)ZrH, Bzind₂(1-Bu-3-MeCp)ZrH, Bzind₂IndZrH, BzindInd₂ZrH,Dbi₂CpZrH, DbiCp₂ZrH, Dbi₂IndZrH, DbiInd₂ZrH, Bzind₂DbiZrH,BzindDbi₂ZrH, BzindDbiCpZrH and BzindDbiIndZrH.

As described above, together with the component (a-2), theorganoaluminum oxy compound above or the like is used as the component(b), and also in this case, the borane compound or borate compound ispreferably used in combination with the organoaluminum oxy compound soas to more enhance the characteristics of the long-chain branchedstructure required of the ethylene-based polymer (B) in the presentinvention. Similarly, it is also preferred to contain the component (c)in addition to the component (a-2) and the component (b).

A specific example of the olefin polymerization catalyst containing, asan essential component, a mixture of a complex having a bridgedbis(indenyl), bridged bis(azulenyl) or bridged bis(cyclopentadienyl)ligand capable of producing a long-chain branched structure as theethylene-based polymer (B) of the present invention and a borane orborate compound as a compound for producing a cationic metallocenecompound together with an organoaluminum oxy compound is an olefinpolymerization catalyst comprising the following component (a-3), amixture of an organoaluminum oxy compound and a borane or boratecompound described in the component (b), and the preferred component(c).

Here, the complex having a bridged bis(indenyl) ligand, a bridgedbis(azulenyl) ligand or a bridged bis(cyclopentadienyl) ligand (referredto as components (a-3-1), (a-3-2) and (a-3-3), respectively) indicates acomplex having a basic skeleton where same or different twocyclopentadienyl rings or same or different two indenyl rings asrepresented by formula [2] in the classification of metallocenecompounds described above in the paragraph of 1-6. (ii) MetalloceneCatalyst are bridged by a bridging group Q¹. The substituent which canbe substituted on the cyclopentadienyl ring, indenyl ring, azulenyl ringor bridging group Q¹ has a high degree of freedom as long as it does notinhibit the basic skeleton structure, and a metallocene complex or thelike having a heteroatom-containing monocyclic or polycyclicheteroaromatic group as a substituent on a ligand of a conjugated5-membered ring structure described, for example, in JP-T-2002-535339may be also suitably used.

[wherein each of A³ and A⁴ represents a ligand having a conjugated5-membered ring structure (A³ and A⁴ may be the same or different in thesame compound). Q¹ represents a bonding group for bridging twoconjugated 5-membered ring ligands at arbitrary positions, M representsa metal atom selected from Group 4 of the periodic table, and each of Xand Y independently represents a hydrogen atom, a halogen atom, ahydrocarbon group, an alkoxy group, an amino group, aphosphorus-containing hydrocarbon group or a silicon-containinghydrocarbon group, which is bonded to M].

As specific examples of the complex having a bridged bis(indenyl) ligandof the component (a-3-1), when the center transition is Zr:

(I) out of the compounds represented by formula [2], compounds where thebonding group Q¹ has, for example, a structure recited below, are shownin Tables a-7 to a-9. In Tables a-7 to a-9, Ind stands for an indenylgroup, and TMS stands for a trimethylsilyl group.

(I-1) When Q¹ is an alkylene group, the complex includes, for example,the compounds shown in Table a-7 below.

TABLE a-7 Q¹ = alkylene group No. Q1 A3 A4 X Y 123a CH2 Ind Ind Cl Cl124a Et Ind Ind Cl Cl 125a Et Ind Ind Cl H 126a Et Ind Ind Cl Me 127a EtInd Ind Cl OMe 128a Et Ind Ind OEt OEt 129a Et Ind Ind Me Me 130a EtH4Ind H4Ind Cl Cl 131a Et 2-Me-Ind 2-Me-Ind Cl Cl 132a Et 2-Et-Ind2-Et-Ind Cl Cl 133a Et 2,4-Me2-Ind 2,4-Me2-Ind Cl Cl 134a Et 4-Ind 4-IndCl Cl 135a Et 2-(2-(5-MeFuryl))Ind 2-(2-(5-MeFuryl))Ind Cl Cl 136a Et2-(2-(5-MeFuryl))-4-Ph-Ind 2-(2-(5-MeFuryl))-4-Ph-Ind Cl Cl 137a Et4-(2,7-Me2-Ind) 4-(2,7-Me2-Ind) Cl Cl 138a Et 2-(2-(5-tBuFuryl)-4-Ph-2-(2-(5-tBuFuryl)-4-Ph- Cl Cl Ind) Ind) 139a Et 2-(2-(5-tBuFuryl)-4-Ph-Ind Cl Cl Ind) 140a Et 4-Ph-Ind 4-Ph-Ind Cl Cl 141a Me2C Ind Ind Cl Cl142a Et Ind Ind Cl H

(I-2) When Q¹ is a silylene group, the complex includes, for example,the compounds shown in Table a-8 below. In Table a-8, Ind stands for anindenyl group, BenInd stands for a benzindenyl group, PhInd stands for aphenylindenyl group, and TMSPh stands for a trimethylsilylphenyl group.

TABLE 8 [a-8] Q¹ = silylene group No. Q1 A3 A4 X Y 143a Me2Si Ind Ind ClCl 144a Me2Si 4,5,6,7-H4Ind 4,5,6,7-H4Ind Cl Cl 145a Me2Si 2-Me-Ind2-Me-Ind Cl Cl 146a Me2Si 2,4-Me2-Ind 2,4-Me2-Ind Cl Cl 147a Me2Si2-Me-4,5,6,7-H4Ind 2-Me-4,5,6,7-H4Ind Cl Cl 148a Me2Si 2-Me-4,5-BenInd2-Me-4,5-BenInd Cl Cl 149a Me2Si 2-Me-4-Ph-Ind 2-Me-4-Ph-Ind Cl Cl 150aMe2Si 2-Me-4,4-Me2-4,5,6,7-H4-4- 2-Me-4,4-Me2-4,5,6,7-H4-4- Cl Clsilaindenyl silaindenyl 151a Me2Si 4-(2-Ph-Ind) 4-(2-Ph-Ind) Cl Cl 152aMe2Si 4-(2-tBuInd) 4-(2-tBuInd) Cl Cl 153a Me2Si 4-(2-Ph-3-MeInd)4-(2-Ph-3-MeInd) Cl Cl 154a PhMeSi Ind Ind Cl Cl 155a PhMeSi4,5,6,7-H4Ind 4,5,6,7-H4Ind Cl Cl 156a Ph2Si Ind Ind Cl Cl 157atetramethyl- Ind Ind Cl Cl disilylene 158a Me2Si2-(2-(5-MeFuryl))-4-PhInd 2-(2-(5-MeFuryl))-4-PhInd Cl Cl 159a Me2Si2-(2-(5-TMSFuryl))-4-PhInd 2-(2-(5-TMSFuryl))-4-PhInd Cl Cl 160a Me2Si2-(2-(5-PhFuryl)-4-PhInd) 2-(2-(5-PhFuryl)-4-PhInd) Cl Cl 161a Me2Si2-(2-(5-Methienyl))-4- 2-(2-(5-Methienyl))-4- Cl Cl PhInd PhInd 162aMe2Si 2-(2-(4,5-Me2Furyl))-4- 2-(2-(4,5-Me2Furyl))-4- Cl Cl PhInd PhInd163a Me2Si 2-(2-BenFuryl)-4-PhInd 2-(2-BenFuryl)-4-PhInd Cl Cl 164aMe2Si 2-(2-BenThienyl)-4-(4- 2-(2-BenThienyl)-4-(4- Cl Cl TMSPh)-IndTMSPh)-Ind 165a Me2Si 2-(2-(5-TMSFuryl))-4-(2- 2-(2-(5-TMSFuryl))-4-(2-Cl Cl Naph)-Ind Naph)-Ind 166a PhMeSi 2-(2-(5-MeFuryl))-4-PhInd2-(2-(5-MeFuryl))-4-PhInd Cl Cl 167a Me2Si 2-(2-(5-MeFuryl))-4-PhInd2-(2-(5-MeFuryl))-4-(4- Cl Cl tBuPh)-Ind 168a Me2Si2-(2-(5-MeFuryl))-4-PhInd 2-(2-(5-MeFuryl))-4-(4- Cl Cl TMSPh)-Ind 169aMe2Si 2-(2-(5-MeFuryl))-4-(4- 2-(2-(5-MeFuryl))-4-(4- Cl Cl tBuPh)-IndTMSPh)-Ind

(I-3) When Q¹ is a hydrocarbon group containing germanium, phosphorus,nitrogen, boron or aluminum, the complex includes, for example, thecompounds shown in Table a-9 below. In Table a-9, Ind stands for anindenyl group, PhInd stands for a phenylindenyl group, and TMSPh standsfor a trimethylsilylphenyl group.

TABLE a-9 No. Q1 A3 A4 X Y 170a Me2Ge Ind Ind Cl Cl 171a MeAl Ind Ind ClCl 172a PhAl Ind Ind Cl Cl 173a PhP Ind Ind Cl Cl 174a EtB Ind Ind Cl Cl175a PhN Ind Ind Cl Cl 176a Me2Ge 2-(2-(5-MeFuryl))-4-2-(2-(5-MeFuryl))- Cl Cl PhInd 4-PhInd 177a MeB 2-(2-(5-MeFuryl))-4-(4-2-(2-(5-MeFuryl))- Cl Cl TMSPh)-Ind 4-(4-TMSPh)-Ind

As specific examples of the complex having a bridged bis(azulenyl)ligand of the component (a-3-2), when the center transition is Zr:

(II) out of the compounds represented by formula [2], compounds wherethe bonding group Q¹ has, for example, a structure recited below, areshown in Tables a-10 to a-12.

(II-1) When Q¹ is an alkylene group, the complex includes, for example,the compounds shown in Table a-10 below. In Tables a-10 to a-12, tBuPhstands for tributylphenyl group, TMSPh stands for a trimethylsilylphenylgroup, NaPh stands for a naphthyl group, BiPh stands for a biphenylgroup. Azu stands for an azulenyl group, and ClPh stands for achlorophenyl group.

TABLE a-10 Q¹ = alkylene group No. Q1 A3 A4 X Y 178a CH22-Et-4-(3-Cl-4-tBuPh)-4- 2-Et-4-(3-Cl-4-tBuPh)-4- Cl Cl HAzu HAzu 179aEt 2-Me-4-(3-Me-4-tBuPh)-4- 2-Me-4-(3-Me-4-tBuPh)-4- Cl Cl HAzu HAzu180a Et 2-Me-4-(3-Cl-4-TMSPh)-4- 2-Me-4-(3-Cl-4-TMSPh)-4- Cl H HAzu HAzu181a Et 2-Me-4-(2-Naph)-4-HAzu 2-Me-4-(2-Naph)-4-HAzu Cl Me 182a Et2-Me-4-(2-F-4-BiPh)-4-HAzu 2-Me-4-(2-F-4-BiPh)-4- Cl OMe HAzu 183a Et2-Me-4-(2-Cl-4-BiPh)-4- 2-Me-4-(2-Cl-4-BiPh)-4- OEt OEt HAzu HAzu 184aEt 2-Me-4-(9-phenanthryl)-4- 2-Me-4-(9-phenanthryl)-4- Me Me HAzu HAzu

(II-2) When Q¹ is a silylene group, the complex includes, for example,the compounds shown in Table a-11 below.

TABLE a-11 Q¹ = silylene group No. Q1 A3 A4 X Y 185a Me2Si2-Me-4-Ph-4-HAzu 2-Me-4-Ph-4-HAzu Cl Cl 186a Me2Si2-Me-4-(4-ClPh)-4-HAzu 2-Me-4-(4-ClPh)-4-HAzu Cl Cl 187a Me2Si2-Me-4-(4-tBuPh)-4-HAzu 2-Me-4-(4-tBuPh)-4-HAzu Cl Cl 188a Me2Si2-Me-4-(4-TMSPh)-4-HAzu 2-Me-4-(4-TMSPh)-4-HAzu Cl Cl 189a Me2Si2-Me-4-(3-Cl-4-tBuPh)-4-HAzu 2-Me-4-(3-Cl-4-tBuPh)-4-HAzu Cl Cl 190aMe2Si 2-Me-4-(3-Me-4-TMSPh)-4-HAzu 2-Me-4-(3-Me-4-TMSPh)-4-HAzu Cl Cl191a Me2Si 2-Me-4-(1-Naph)-4-HAzu 2-Me-4-(1-Naph)-4-HAzu Cl Cl 192aMe2Si 2-Et-4-(4-ClPh)-4-HAzu 2-Et-4-(4-ClPh)-4-HAzu Cl Cl 193a Me2Si2-Me-4-(4-Cl-2-Naph)-4-HAzu 2-Me-4-(4-Cl-2-Naph)-4-HAzu Cl Cl 194a Me2Si2-nPr-4-(3-Cl-4-TMSPh)-4- 2-nPr-4-(3-Cl-4-TMSPh)-4- Cl Cl HAzu HAzu

(II-3) When Q¹ is a hydrocarbon group containing germanium, phosphorus,nitrogen, boron or aluminum, the complex includes, for example, thecompounds shown in Table a-12 below.

TABLE a-12 No. Q1 A3 A4 X Y 195a Me2Ge 2-Me-4-(2-F-4-BiPh)-2-Me-4-(2-F-4-BiPh)- Cl Cl 4-HAzu 4-HAzu 196a PhAl 2-Me-4-(2-F-4-BiPh)-2-Me-4-(2-F-4-BiPh)- Cl Cl 4-HAzu 4-HAzu 197a Me2Ge 2-Me-4-(4-tBuPh)-4-2-Me-4-(4-tBuPh)-4- Cl Cl HAzu HAzu

As specific examples of the complex having a bridgedbis(cyclopentadienyl) ligand of the component (a-3-3), when the centertransition is Zr:

(II) out of the compounds represented by formula [2], compounds wherethe bonding group Q¹ has, for example, a structure recited below, areshown in Tables a-13 to a-16. In Tables a-13 to a-16, Cp stands for acyclopentadienyl group, TMS stands for trimethylsilyl, and Flu standsfor fluorenyl.

(III-1) When Q¹ is an alkylene group, the complex includes, for example,the compounds shown in Table a-13 below.

TABLE a-13 Q¹ = alkylene group No. Q1 A3 A4 X Y 198a Et 2,4-Me2Cp3′,5′-MeCp Cl Cl 199a Et 2-Me-4-tBuCp 3′-tBu-5′-MeCp Cl Cl 200a Et2,3,5-Me3Cp 2′,4′,5′-Me3Cp Cl Cl 201a Me2C 2,4-Me2Cp 3′,5′-Me2Cp Cl Cl202a CH2 Cp 3,4-Me2Cp Cl Cl 203a CH2 Cp 3,4-Me2Cp Cl H 204a CH2 Cp3,4-Me2Cp Me Me 205a CH2 Cp 3,4-Me2Cp Ph Ph 206a CH2 Cp TMSCp Cl Cl 207aCH2 Cp Me4Cp Cl Cl 208a Me2C Cp 3,4-Me2Cp Cl Cl 209a Me2C Cp Me4Cp Cl Cl210a Me2C Cp Flu Cl Cl 211a Me2C 2-MeCp Flu Cl Cl 212a Me2C 3-tBuCp FluCl Cl 213a Me2C 2,5-Me2Cp 3′,4′-Me2Cp Cl Cl 214a Me2C 2,5-Me2Cp Flu ClCl 215a Et Cp 3,5-Me2Cp Cl Cl 216a Et Cp Flu Cl Cl 217a Et 2,5-Me2Cp FluCl Cl 218a Et 2,5-Et2Cp Flu Cl Cl 219a Ph2C Cp 3,4-Et2Cp Cl Cl 220acyclohexylidene Cp Flu Cl Cl 221a cyclohexylidene 2,5-Me2Cp 3′,4′-Me2CpCl Cl 222a Et 2-(2-(5-MeFuryl))Cp 2-(2-(5-MeFuryl))Cp Cl Cl 223a Et2-(2-(5-MeFuryl))-4-PhCp 2-(2-(5-MeFuryl))-4- Cl Cl PhCp 224a Et2-(2-(5-tBuFuryl))Cp 2-(2-(5-tBuFuryl))Cp Cl Cl 225a Et2-(2-(5-tBuFuryl))-4- Cp Cl Cl PhCp

(II-2) When Q¹ is a silylene group, the complex includes, for example,the compounds shown in Tables a-14 and a-15 below.

TABLE a-14 Q¹ = silylene group No. Q A3 A4 X Y 227a Me2Si 2,4-Me2Cp3′,5′-MeCp Cl Cl 228a PhMeSi 2,4-Me2Cp 3′,5′-MeCp Cl Cl 229a PhMeSi2,3,5-Me3Cp 2′,4′,5′-Me3Cp Cl Cl 230a PhMeSi Me4Cp Me4Cp Cl Cl 231atetramethyl- Cp Cp Cl Cl disilylene 232a Me2Si Cp 3,4-Me2Cp Cl Cl 233aMe2Si Cp Me3Cp Cl Cl 234a Me2Si Cp Me4Cp Cl Cl 235a Me2Si Cp 3,4-Et2CpCl Cl 236a Me2Si Cp Et3Cp Cl Cl 237a Me2Si Cp Me4Cp Cl Cl 238a Me2Si CpFlu Cl Cl 239a Me2Si 3-tBuCp Flu Cl Cl 240a Me2Si Cp 2,7-tBu2Flu Cl Cl241a Me2Si Cp H8Flu Cl Cl 242a Me2Si 2-MeCp Flu Cl Cl 243a Me2Si2,5-Me2Cp Flu Cl Cl 244a Me2Si 2-EtCp Flu Cl Cl 245a Me2Si 2,5-Et2Cp FluCl Cl 246a Et2Si 2-MeCp 2′,7′-tBu2Flu Cl Cl 247a Me2Si 2,5-Me2Cp2′,7′-tBu2Flu Cl Cl 248a Me2Si 2-EtCp 2′,7′-tBu2Flu Cl Cl 249a Me2SiEt2Cp 2′,7′-tBu2Flu Cl Cl 250a Me2Si Et2Cp H8Flu Cl Cl 251a Me2Si Me2CpH8Flu Cl Cl 252a Me2Si EtCp H8Flu Cl Cl 253a Me2Si Et2Cp H8Flu Cl Cl

TABLE a-15 Q¹ = silylene group (continued) No. Q A3 A4 X Y 254a Me2Si2-(2-(5-tBuFuryl))Cp 2-(2-(5-tBuFuryl))Cp Cl Cl 255a Me2Si2-(2-(5-TMSFuryl))Cp 2-(2-(5-TMSFuryl))Cp Cl Cl 256a Me2Si2-(2-(5-PhFuryl))Cp 2-(2-(5-PhFuryl))Cp Cl Cl 257a Me2Si2-(2-(5-MeThienyl))Cp 2-(2-(5-MeThienyl))Cp Cl Cl 258a Me2Si2-(2-(4,5-Me2Furyl))Cp 2-(2-(4,5-Me2Furyl))Cp Cl Cl 259a Me2Si2-(2-BenFuryl)Cp 2-(2-BenFuryl)Cp Cl Cl 260a Me2Si2-(2-BenThienyl)-4-(4-TMSPh)Cp 2-(2-BenThienyl)-4-(4- Cl Cl TMSPh)Cp261a Me2Si 2-(2-(5-TMSFuryl))Cp 2-(2-(5-TMSFuryl))Cp Cl Cl 262a PhMeSi2-(2-(5-MeFuryl))Cp 2-(2-(5-MeFuryl))Cp Cl Cl 263a Me2Si2-(2-(5-MeFuryl))Cp Cp Cl Cl 264a Me2Si 2-(2-(5-MeFuryl))-4-PhCp2-(2-(5-MeFuryl))Cp Cl Cl 265a Me2Si 2-(2-(5-MeFuryl))Cp 3-MeCp Cl Cl

(II-3) When Q¹ is a hydrocarbon group containing germanium, phosphorus,nitrogen, boron or aluminum, the complex includes, for example, thecompounds shown in Table a-16 below.

TABLE a-16 No. Q1 A3 A4 X Y 266a Me2Ge Cp Flu Cl Cl 267a PhN Cp Flu ClCl 268a Me2Ge 2-(2-(5-MeFuryl))Cp 2-(2-(5-MeFuryl))Cp Cl Cl 269a MeB2-(2-(5-MeFuryl))-4- 2-(2-(5-MeFuryl))-4- Cl Cl TMSCp TMSCp

Thanks to a catalyst where a mixture of an organoaluminum oxy compoundand a borane compound or the like is combined with a complex having abridged bis(indenyl) ligand, a bridged bis(azulenyl) ligand or a bridgedbis(cyclopentadienyl) ligand, which is defined by the compounds above, along-chain branched structure suitable as the ethylene-based polymer (B)of the present invention is imparted to an ethylene-based polymer (B).

In the foregoing pages, three catalyst systems, that is, a catalystsystem containing, as an essential component, a complex having a bridged(cyclopentadienyl)(indenyl) ligand or the like, a catalyst systemcontaining, as an essential component, a complex having a benzindenylligand or the like, and a catalyst system using a mixture of a complexhaving a bridged bis(indenyl) ligand or a bridged bis(cyclopentadienyl)ligand, which is a metallocene complex, and a borane or borate compoundthat is a compound capable of producing a cationic metallocene compoundtogether with an organoaluminum oxy compound, are described as specificpreferred examples of the olefin polymerization catalyst for producing along-chain branched structure suitable as the ethylene-based polymer (B)of the present invention. Among these, a catalyst system containing, asan essential component, a complex having a bridge(cyclopentadienyl)(indenyl) ligand or the like and a catalyst systemusing a mixture of a complex having a bridged bis(indenyl) ligand or abridged bis(cyclopentadienyl) ligand, which is a metallocene complex,and a borane or borate compound that is a compound capable of producinga cationic metallocene compound together with an organoaluminum oxycompound, are more preferred, and a catalyst system containing, as anessential component, a complex having a bridged(cyclopentadienyl)(indenyl) ligand or the like is still more preferred.

In the present invention, the production of the ethylene-based polymer(B) is performed by contacting ethylene with the olefin polymerizationcatalyst (i) to (iv), more preferably (i), (ii) or (iv), still morepreferably (i) or (ii), yet still more preferably (ii) the metallocenecatalyst, thereby polymerizing or copolymerizing the ethylene. As theolefin polymerization catalyst, a plurality of kinds of catalyst may beselected from (i) to (iv) and used. At the time of performingpolymerization or copolymerization of ethylene, all descriptions of thepolymerization method, ethylene raw material, polymerization medium,polymerization temperature and the like, polymerization process and thelike, and scavenger in the paragraph of Production Method ofEthylene-Based Polymer (A) above may be referred to. However, it isneedless to say that these various conditions must be optimally set bytaking into account various characteristics required of theethylene-based polymer (B) and the characteristics of the olefinpolymerization catalyst used. For example, in the case of desiring foran ethylene-based polymer (B) having a lower MFR and a lower density,the chain transfer agent concentration is set relatively low, theα-olefin concentration is set relatively high, in order to prevent apolymer in the production process from a trouble such asfixing•blocking, various operation temperatures are set on the lowtemperature side as appropriate for the melting temperature or the likeof the polymer, a low-molecular-weight hydrocarbon solvent hardlycausing dissolution of the polymer such as propane and butane, isselected in the slurry polymerization, a gas phase polymerization notusing a solvent is selected, or solution polymerization treating thepolymer in the molten state is selected. Also, in the case of intendingto impart distinctive long-chain branch characteristics, it is preferredto aggressively select a low monomer concentration condition, a highpolymer concentration condition, a low scavenger concentrationcondition, a high temperature polymerization condition, a long timepolymerization condition or the like so that the chain transfer reactionexcept for hydrogen can be accelerated.

(3) Other Components (C)

In the polyethylene-based resin composition of the present invention, aslong as the purpose of the present invention is not impaired, thefollowing substances can be blended as an optional component, inaddition to the ethylene-based polymer (A) and the ethylene-basedpolymer (B), which are essential components.

3-1. Other Ethylene-Based Polymers

In addition to the ethylene-based polymer (A) and the ethylene-basedpolymer (B), various ethylene-based polymers and modification productsthereof, such as high-density polyethylene, low-density polyethylene,high-pressure polyethylene, polar monomer graft-modified polyethylene,ethylene-based wax, ultrahigh molecular weight polyethylene andethylene-based elastomer, can be used. Addition of a high-densitypolyethylene is preferred for enhancing the stiffness, heat resistance,impact strength and the like. Addition of a low-density polyethylene ispreferred for enhancing the flexibility, impact strength, easyadhesiveness, transparency, low-temperature strength and the like.Addition of a high-pressure polyethylene is preferred for enhancing theflexibility, easy adhesiveness, transparency, low-temperature strength,moldability and the like. Addition of a polar monomer graft-modifiedpolyethylene such as maleic acid-modified polyethylene, ethylene.acrylicacid derivative copolymer and ethylene.vinyl acetate copolymer ispreferred for enhancing the flexibility, easy adhesiveness,colorability, affinity for various materials, gas barrier property andthe like. Addition of an ethylene-based wax is preferred for enhancingthe colorability, affinity for various materials, moldability and thelike. Addition of an ultrahigh molecular weight polyethylene ispreferred for enhancing the mechanical strength, abrasion resistance andthe like. Addition of an ethylene-based elastomer is preferred forenhancing the flexibility, mechanical strength, impact strength and thelike.

3-2. Other Olefin-Based Polymer

As an olefin-based polymer other than an ethylene-based polymer, forexample, a polypropylene-based resin, a higher olefin-based resin suchas polybutene, polyisobutene and polyhexene, an olefin-based rubber, apolybutadiene-based resin such as butadiene, isoprene and chloroprene, apolystyrene-based resin such as polystyrene and poly-α-methylstyrene,various cyclic olefin-based resin, and modification products thereof canbe used.

3-3. Other Resins

Various resins containing, as a main component, a polymer except for theabove-described ethylene-based polymer or other olefin-based polymerscan be used. Specific examples thereof include various nylon resins,various polyamides, polyethylene terephthalate (PET), polybutyleneterephthalate (PBT), various polyesters, a polycarbonate resin, EVOH,EVA, PMMA, PMA, various engineering plastics, polylactic acid,celluloses, natural rubbers, polyurethane, vinyl chloride, fluororesinsuch as Teflon (registered trademark), and an inorganic polymer such assilicon resin.

3-4. Additive

All additives may be appropriately used individually or in combinationof two or more thereof. Specifically, for example, an antioxidant (e.g.,phenol type, phosphorus type, sulfur type), an ultravioletabsorber-ultraviolet inhibitor, a light stabilizer•weatherproofingagent, a lubricant, an antistatic agent, an antifogging agent, anantiblocking agent, a processing aid such as dispersant, a color pigment(organic or inorganic pigment), a pearl pigment, a polarizing pearlpigment, a crosslinking agent, a blowing agent, a neutralizer, a heatstabilizer, a crystallization nucleating agent, an inorganic or organicbulking agent•filler [such as calcium carbonate, talc, metal powder(e.g., aluminum copper, iron, lead), silica dust, diatomaceous earth,alumina, gypsum, mica, clay, asbestos, graphite, carbon black andtitanium oxide], and a flame retardant can be used.

(4) Mixing of Respective Components Constituting Polyethylene-BasedResin Composition of the Present Invention

The polyethylene-based resin composition of the present invention isproduced by mixing the ethylene-based polymer (A), the ethylene-basedpolymer (B), which are essential components, and the substance (C) as anoptional component.

The blending ratio of respective components is from 41 to 99 wt % of theethylene-based polymer (A) and from 1 to 59 wt % of the ethylene-basedpolymer (B), preferably from 61 to 96 wt % of the ethylene-based polymer(A) and from 4 to 39 wt % of the ethylene-based polymer (B), morepreferably from 69 to 96 wt % of the ethylene-based polymer (A) and from4 to 31 wt % of the ethylene-based polymer (B), still more preferablyfrom 69 to 91 wt % of the ethylene-based polymer (A) and from 9 to 31 wt% of the ethylene-based polymer (B), yet still more preferably from 75to 89 wt % of the ethylene-based polymer (A) and from 11 to 25 wt % ofthe ethylene-based polymer (B). If the proportion of the ethylene-basedpolymer (A) is too large, the polyethylene-based resin composition orits molded product may be reduced in the impact resistance ortransparency and out of the moldability, the melt tension decreases,whereas if the proportion is small, the stiffness may be deterioratedand out of the moldability, the melt extrudability becomes bad. If theproportion of the ethylene-based polymer (B) is too large, thepolyethylene-based resin composition or its molded product may bereduced in the stiffness or transparency and out of the moldability, themelt extrudability becomes bad, whereas if the proportion is small, thetear strength, impact strength and transparency may not be improved andout of the moldability, the melt tension decreases. Incidentally, theproportion of the substance (C) as an optional component isappropriately set as long as the purpose of the present invention is notimpaired, but the proportion is usually from 0 to 49 wt % andparticularly, in using various additives recited in Item 3-4 above, allexisting examples related to application to known polyethylene-basedresins, polyethylene-based resin compositions and their molded productmay be referred to.

In producing the polyethylene-based resin composition of the presentinvention by mixing the ethylene-based polymer (A), the ethylene-basedpolymer (B), which are essential components, and the substance (C) as anoptional component, the mixing method therefor or the apparatus used isnot particularly limited, but usually, these components are mixed usinga Henschel mixer, a super-mixer, a tumbler-type mixer or the like,kneaded under heating, for example, in a mixing extruder such as single-or twin-screw extruder, kneader and plunger extruder, or in a Banburymixer, and then pelletized. The kneading under heating can be performedin the presence or absence of a liquid, a solvent or a gas. The order ofmixing those components is also not particularly limited, and, forexample, the following methods (D-1) to (D-4) may be recited:

(D-1) a method where the ethylene-based polymer (A), the ethylene-basedpolymer (B) and the optional substance (C) all in the solid state,preferably all in the powder, particle or pellet state, are previouslycontacted and mixed with each other, and the mixture is put into a moreuniform state by kneading under heating;

(D-2) a method where any one or more components of the ethylene-basedpolymer (A), the ethylene-based polymer (B) and the optional substance(C) are put into a molten state, a dissolved state or a liquid state andthen contacted and mixed with other components, and the mixture isfurthermore put into a more uniform state by kneading under heating;

(D-3) a method where any two components of the ethylene-based polymer(A), the ethylene-based polymer (B) and the optional substance (C) arepreviously kneaded under heating by, for example, the method (D-1) or(D-2) above, and the mixture obtained by the kneading under heating isfurther kneaded under heating with the remaining one component andthereby put into a more uniform state, and

(D-4) a method where any one component of the ethylene-based polymer(A), the ethylene-based polymer (B) and the optional substance (C) ispreviously kneaded under heating with, individually and separately, bothof the remaining two components, for example, by the method (D-1) or(D-2), and the mixtures obtained by the kneading under heating isfurther kneaded under heating and thereby put into a more uniform state.

(5) Physical Properties of Polyethylene-Based Resin Composition of thePresent Invention

The polyethylene-based resin composition of the present invention isproduced by mixing the ethylene-based polymer (A), the ethylene-basedpolymer (B), which are essential components, and the substance (C) as anoptional component, for example, by the mixing method of (D-1) to (D-4)above, and as for the physical properties, the composition as a wholemust satisfy the ranges of MFR and density described below.

5-1. MFR

The melt flow rate (MFR) of the polyethylene-based resin composition ofthe present invention is from 0.05 to 50 g/10 min, preferably from 0.1to 20 g/10 min, more preferably from 0.3 to 10 g/10 min, still morepreferably from 0.4 to 5.0 g/10 min, yet still more preferably from 0.5to 3.0 g/10 min. If MFR is less than 0.05 g/10 min, the flowability ofthe polyethylene-based resin composition is bad, and this maydisadvantageously require a too high motor load of the extruder or leadto poor spreadability. If MFR exceeds 50 g/10 min, thepolyethylene-based resin composition or its molded product becomesinferior in the mechanical strength such as impact strength, tearstrength and tensile strength or in the moldability, and this is notpreferred. Incidentally, MFR indicates a value when measured under thesame conditions as the condition (A-1) above.

5-2. Density

The density of the polyethylene resin composition of the presentinvention is from 0.910 to 0.960 g/cm³, preferably from 0.910 to 0.950g/cm³, more preferably from 0.916 to 0.940 g/cm³, still more preferablyfrom 0.919 to 0.938 g/cm³, yet still more preferably from 0.920 to 0.936g/cm³, and most preferably from 0.921 to 0.934 g/cm³.

If the density of the polyethylene resin composition is less than 0.910g/cm³, the polyethylene-based resin composition or its molded productmay be reduced in the stiffness or become sticky and when the product isa molded product having a small thickness, such as film and sheet, aswell as various problems in using the product, a problem isdisadvantageously brought about in the step of winding up the product orthe post-processing step such as surface printing•lamination, leading topoor suitability for automatic bag machine, or when the product is amolded product having a large wall thickness, such as pipe and variouscontainers, since the product is too soft and undergoes deformation, thewall thickness must be disadvantageously designed to be larger thannecessary. Also, if the density of the polyethylene resin compositionexceeds 0.960 g/cm³, the impact strength of the polyethylene-based resincomposition or its molded product may be reduced and the transparencymay also become bad. Incidentally, the density indicates a value whenmeasured under the same conditions as the condition (A-2) above.

[II] Molded Product and Use of Polyethylene-Based Resin Composition ofthe Present Invention

The molded product of the polyethylene-based resin composition of thepresent invention is produced by molding the polyethylene-based resincomposition of the present invention described in [I] above, and as forthe molding method, all of molding methods for a polyolefin-based resinor a polyolefin-based resin composition, such as injection molding,compression-injection molding, rotational molding, extrusion molding,hollow molding and blow molding, which are conventionally known, may bereferred to.

The molded product as used in the present invention indicates aprocessed article or a shaped article obtained by processing or shapingthe polyethylene-based resin composition into an appropriate formaccording to the intended use, and specific examples thereof include afilm, a bag, a sheet, a coating, a fiber, a yarn, a container, a tube, apipe, a covering material, a lid, a cap, a box, sundry articles, toys,medical device parts, a bead, a fine particle, and a foamed product.These articles may have a multilayer structure or may be a compositearticle with other members. As for these molded articles of thepolyethylene-based resin composition of the present invention, specificexamples of use thereof include a standardized bag mandated by thedimensional standard, such as bag-in-paper bag and garbage bag, a heavyduty sack, a wrapping film, a sugar bag, a rice bag, an oily substancepackaging bag, a food packaging film in a bag for packaging a waterymaterial such as pickles, an agricultural film, a laminate with varioussubstrates such as nylon, polyester, metal foil and saponifiedethylene-vinyl acetate copolymer, a foamed body, and a molded productthereof, and applications of a molded product of knownpolyethylene-based resins and polyethylene-based resin compositions,such as bag-in-box, detergent container, edible oil container, retortcontainer, medical container, chemical container, solvent container,agricultural container, various plastic bottle products, hollowcontainer (e.g., kerosene can, drum, fuel tank), infusion bag, varioustubes, pipe (e.g., water pipe, gas pipe), Tupperware container cover,bottle cap and container, may be referred to.

The molding method for the molded product of the present invention isnot particularly limited as long as it is a method capable ofeffectively utilizing excellent molding characteristics, variousmechanical properties and transparency of the polyethylene-based resincomposition of the present invention, but in the case of a film, bag orsheet as an example of the application in which the polyethylene-basedresin composition of the present invention is intended to be mainlyused, preferred examples of the molding method, molding conditions anduse include, specifically, various inflation molding methods, T-die filmmolding methods, calendar molding methods, multilayer film moldingmethods using a multilayer coextrusion molding machine or laminationprocessing, and various applications, which are described in detail, forexample, in JP-A-2007-197722, JP-A-2007-177168, JP-A-2007-177187 andJP-A-2010-31270. Of course, a gas other than air, or a liquid can beused as a cooling medium in the inflation molding and may be also usedin special inflation such as stretch (inflation simultaneous biaxialstretching) molding and multi-stage blow-molding.

The thus-obtained film (or sheet) product is not particularly limited inits sheet, and the suitable thickness differs depending on the moldingmethod-conditions. For example, in the case of inflation molding, thethickness is approximately from 5 to 300 μm, and in the case of T-diemolding, a film (or sheet) having a thickness of approximately from 5 μmto 5 mm can be obtained. Similarly, in the case of hollow containers asan example of the application in which the polyethylene-based resincomposition of the present invention is intended to be mainly used,preferred examples of the molding method, molding conditions and usedinclude, specifically, various hollow molding methods and blow moldingmethods and various applications, which are described in detail, forexample, in JP-A-2004-18812, JP-A-2009-143079 and JP-A-2009-173889.Similarly, in the case of a pipe, a covering material, a cover, caps, abox and sundries as an example of the application of thepolyethylene-based resin composition of the present invention, preferredexamples of the molding method, molding conditions and used include,specifically, various molding methods and various applications, whichare described in detail, for example, in JP-A-2007-2235,JP-A-2007-177183 and JP-A-2002-60559. Furthermore, as otherapplications, the polyethylene-based resin composition may be used as amodifier, for example, to enhance the moldability, enhance themechanical strength, impart low-temperature resistance or impartlow-temperature adhesiveness, by blending a small amount of thecomposition with another polyethylene-based resin or polyethylene-basedresin composition or with a polyolefin-based resin such aspolypropylene-based resin.

[III] Ethylene-Based Polymer

A second aspect of the present invention relates to an ethylene-basedpolymer having a developed long-chain branched structure and exhibitingexcellent moldability. The second aspect of the present invention isdescribed below item by item.

The ethylene-based polymer of the present invention satisfies all of theconditions (B-1′) to (B-8) described below.

III-1. Condition (B-1′)

MFR_(B) of the ethylene-based polymer in the present invention is from0.001 to 200 g/10 min, preferably from 0.01 to 100 g/10 min, morepreferably from 0.05 to 50 g/10 min, still more preferably from 0.1 to50 g/10 min, and most preferably from 0.1 to 10 g/10 min. If MFR_(B) isless than 0.001 g/10 min. the ethylene-based polymer may be inferior inthe moldability, particularly in the melt flowability and spreadability,and uniform mixing with another resin may become difficult,disadvantageously giving rise to production of an appearance failuresuch as gel, grain and fisheye or reduction in the impact strength ortransparency. If MFR_(B) exceeds 200 g/10 min, the ethylene-basedpolymer or a composition obtained by mixing the polymer with anotherresin may be reduced in the mechanical strength such as impact strength,tear strength and tensile strength and this is not preferred.Incidentally, MFR indicates a value when measured under the sameconditions as in the condition (A-1).

III-2. Condition (B-2″)

The density_(B) of the ethylene-based polymer in the present inventionis from 0.880 to 0.970 g/cm³, preferably from 0.891 to 0.960 g/cm³, morepreferably from 0.895 to 0.950 g/cm³, still more preferably from 0.900to 0.934 g/cm³, and most preferably from 0.900 to 0.925 g/cm³. When thedensity_(B) is in this range, the ethylene-based polymer or its moldedproduct is excellent in the balance between impact strength andstiffness and in the transparency. On the other hand, if the density_(B)is less than 0.880 g/cm³, the stiffness is reduced and when the productis a molded product having a small thickness, such as film and sheet, aswell as various problems in using the product, a problem isdisadvantageously brought about in the step of winding up the product orthe post-processing step such as surface printing•lamination or when theproduct is a molded product having a large wall thickness, such as pipeand various containers, since the product is too soft and undergoesdeformation, the wall thickness must be disadvantageously designed to belarger than necessary. In addition, the polymer is heavily sticky evenat room temperature and difficult to handle in the blending step withanother resin, disadvantageously giving rise to product sticking of theresin composition, and furthermore, the compatibility with the anotherresin may be reduced to deteriorate the impact strength or transparencydue to phase separation. Also, if the density_(B) exceeds 0.970 g/cm³,the impact strength or transparency is deteriorated and this is notpreferred. In the case of using the polymer as a modifier to enhance thestrength of another resin, the density of the ethylene-based polymer inthe present invention is preferably from 0.900 to 0.910 g/cm³.Incidentally, the density indicates a value when measured under the sameconditions as the condition (A-2) above.

III-3. Condition (B-3)

The [Mw/Mn]_(B) of the ethylene-based polymer in the present inventionis from 2.0 to 10.0, preferably from 2.0 to 6.0, more preferably from2.5 to 5.6, still more preferably from 2.9 to 4.5, yet still morepreferably from 3.2 to 4.0. If [Mw/Mn]_(B) is less than 2.0, the polymermay be reduced in the molding characteristics or may be difficult to mixwith another resin and therefore, this should be avoided. If [Mw/Mn]_(B)exceeds 10.0, the ethylene-based polymer, the mixed resin compositionwith another resin or the molded product may lack the impact strength,be deteriorated in the transparency or become sticky, and this is notpreferred. Incidentally, Mw/Mn indicates a value measured under the sameconditions as the condition (A-3) above.

III-4. Condition (B-4′)

The [λmax(2.0)]_(B) of the ethylene-based polymer in the presentinvention is from 1.2 to 30.0, preferably from 1.5 to 20.0, morepreferably from 2.0 to 10.0, still more preferably from 2.4 to 6.0, yetstill more preferably from 3.0 to 5.0. If [λmax(2.0)]_(B) is less than1.2, the ethylene-based polymer, the mixed resin composition withanother resin or the molded product may lack the flowability or melttension and be deteriorated in the molding characteristics. If[λmax(2.0)]_(B) exceeds 30.0, the flowability and melt tension may beexcellent, but the ethylene-based polymer or the like may bedisadvantageously reduced in the impact strength or transparency.Incidentally, λmax(2.0) indicates a value when measured under the sameconditions as the condition (A-4) above. The effect of the elongationalflow characteristics of the polyethylene on its moldability ormechanical properties of the molded product is as already describedabove in the condition (A-4) or condition (B-4).

III-5. Condition (B-5)

As regards the ethylene-based polymer in the present invention, the[λmax(2.0)]_(B)/[λmax(0.1)]_(B) defined in the condition (B-5) of Item2.5 above is from 1.2 to 10.0, preferably from 1.3 to 5.0, morepreferably from 1.4 to 4.0, still more preferably from 1.5 to 3.0. If[λmax(2.0)]_(B)/[λmax(0.1)]_(B) is less than 1.2, the ethylene-basedpolymer, the mixed resin composition with another resin or the moldedproduct may be in a non-uniform molten state or may have a thermallyunstable structure, or reduction in the impact strength or deteriorationof the transparency may be caused due to strength anisotropy of themolded product, which is attributable to the presence of a significantlyelongated long-chain branched structure, and this is not preferred. If[λmax(2.0)]_(B)/[λmax(0.1)]_(B) exceeds 10.0, the melt tension andflowability during molding may be excellent, but the ethylene-basedpolymer, the mixed resin composition with another resin or the moldedproduct may be disadvantageously reduced in the impact strength ortransparency.

III-6. Condition (B-6)

The ethylene-based polymer of the present invention is a polymerproduced by an ethylene polymerization reaction using a catalystcontaining a transition metal, and all of the matters described in thecondition (B-6) of Item 2.6 apply.

III-7. Condition (B-7)

As regards the ethylene-based polymer in the present invention, theabove-described g_(C)′ is from 0.30 to 0.70, and all of the mattersdescribed in the condition (B-7) of Item 2.7 above apply. The g_(C)′value is preferably from 0.30 to 0.59, more preferably from 0.35 to0.55, still more preferably from 0.35 to 0.50, yet still more preferablyfrom 0.35 to 0.45. If the g_(C)′ value exceeds 0.70, the ethylene-basedpolymer, the mixed resin composition with another resin or the moldedproduct may disadvantageously lack the moldability or transparency. Ifthe g_(C)′ value is less than 0.30, the moldability of theethylene-based polymer or the like may be improved, but the impactstrength of the molded product may be reduced or the transparency may bedeteriorated, and this is not preferred. Incidentally, the g_(C)′ valueor the W_(C) value in the next paragraph indicates a value when measuredunder the same conditions as the condition (B-7) of Item 2.7 or thecondition (B-8) of Item 2.8 above.

III-8. Condition (B-8)

As regards the ethylene-based polymer in the present invention, theabove-described W_(C) is from 0.01 to 30.0%, and all of the mattersdescribed in the condition (B-8) of Item 2.8 above apply. The W_(C)value is more preferably from 0.02 to 10.0%, still more preferably from0.05 to 8.0%, yet still more preferably from 0.10 to 6.0%, and mostpreferably from 0.11 to 4.0%. If the W_(C) value is less than 0.01%, theethylene-based polymer or the mixed resin composition with another resinmay be inferior in the moldability or the ethylene-based polymer or thelike may lack the transparency, and this is not preferred. If the W_(C)value exceeds 30.0%, the ethylene-based polymer or the like may beenhanced in the melt tension out of the moldability, but the meltflowability may be excessively reduced to disadvantageously cause aproblem in the production or molding of the ethylene-based polymer orthe like. Furthermore, the impact strength or the transparency of themolded product may be deteriorated, and this is not preferred.

III-9. Condition (B-9)

The ethylene-based polymer in the present invention preferably furthersatisfies the following condition (B-9), in addition to the condition(B-1) to the condition (B-8) defined in Items III-1 to III-8 above.

The condition (B-9) is that in the TREF measurement using anorthodichlorobenzene solvent, the content (W⁻¹⁵; unit: wt %) ofcomponents eluted at −15° C. is 2.0 wt % or less.

The W⁻¹⁵ value is preferably 0.9 wt % or less, more preferably 0.6 wt %or less, still more preferably 0.5 wt %, yet still more preferably 0.4wt %, and most preferably 0.3 wt %. The lower limit of the W⁻¹⁵ value ispreferably 0.0 wt %, that is, the components are not detected. If theW⁻¹⁵ value exceeds 2.0 wt %, the ethylene-based polymer, the mixed resincomposition with another resin or the molded product may lack the impactstrength, be deteriorated in the transparency or become sticky, and thisis not preferred. Also, the compatibility with another resin may becomebad, and this may disadvantageously give rise to deterioration of theimpact strength or transparency. In the present invention, the W⁻¹⁵value is measured by the following method.

A sample is dissolved in orthodichlorobenzene (containing 0.5 mg/mL BHT)at 140° C. to prepare a solution, and the solution is introduced into aTREF column at 140° C., then cooled to 100° C. at a temperature droprate of 8° C./min, further cooled to −15° C. at a temperature drop rateof 4° C./min and held for 60 minutes. Thereafter, orthodichlorobenzene(containing 0.5 mg/mL BHT) as a solvent is flowed through the column ata flow rate of 1 mL/min to elute components dissolved in theorthodichlorobenzene at −15° C. in the TREF column for 10 minutes, andthen the column temperature is raised linearly to 140° C. at atemperature rise rate of 100° C./hr to obtain an elution curve.

Apparatus: (TREF Part)

TREF Column: Stainless steel-made column of 4.3 mmφ×150 mm

Column packing material: Inert glass bead of 100 μm

Heating system: Aluminum heating block

Cooling system: Peltier element (cooling of Peltier element is watercooling)

Temperature distribution: ±0.5° C.

Temperature regulator: programmable digital controller, KP 1000,manufactured by Chino Corporation

(Valve Part)

Heating system: Air bath oven

Temperature at measurement: 140° C.

Temperature distribution: ±1° C.

Valve: Six-way valve, four-way valve

(Sample Injection Part)

Injection system: Loop injection system

Injection amount: Loop size, 0.1 ml

Injection port heating system: Aluminum heating block

Temperature at measurement: 140° C.

(Detector Part)

Detector: Wavelength-fixed infrared detector, MIRAN 1A, manufactured byFOXBORO

Detection wavelength: 3.42 m

High-temperature flow cell: Micro-flowcell for LC-IR, optical pathlength: 1.5 mm, window shape: oval of 2φ×4 mm, synthetic sapphireaperture plate

Temperature at measurement: 140° C.

(Pump Part)

Liquid delivery pump: SSC-3461 pump, manufactured by Senshu KagakuMeasurement Conditions:

Solvent: o-Dichlorobenzene (containing 0.5 mg/mL of BHT)

Sample concentration: 5 mg/mL

Sample injection amount: 0.1 mL

Solvent flow velocity: 1 mL/min

[IV] Olefin Polymerization Catalyst Component of the Present Invention

A third aspect of the present invention relates to an olefinpolymerization catalyst component containing a metallocene compoundhaving a specific structure, which is useful for producing ametallocene-based polyolefin or metallocene-based polyethylene having asufficient number of long-chain branches having an appropriate length,and an olefin polymerization catalyst containing the component. Thethird aspect of the present invention is described below item by item.

The olefin polymerization catalyst component of the present invention isan olefin polymerization catalyst component containing the followingcomponent (A-1b) and component (A-2b), or an olefin polymerizationcatalyst component containing the following component (Ac).

IV-1. Olefin Polymerization Catalyst Component Containing Component(A-1b) and Component (A-2b) of the Present Invention

A first embodiment of the olefin polymerization catalyst component ofthe present invention contains the components (A-1b) and (A-2b) definedbelow as essential components.

Component (A-1b): a metallocene compound represented by the followingformula (1b):

[in formula (1b), M^(1b) represents any one transition metal of Ti, Zrand Hf; each of X^(1b) and X^(2b) independently represents a hydrogenatom, a halogen atom, a hydrocarbon group having a carbon number of 1 to20, a hydrocarbon group containing an oxygen atom or a nitrogen atom andhaving a carbon number of 1 to 20, a hydrocarbon group-substituted aminogroup having a carbon number of 1 to 20, or an alkoxy group having acarbon number of 1 to 20; each of Q^(1b) and Q^(2b) independentlyrepresents a carbon atom, a silicon atom or a germanium atom, eachR^(1b) independently represents a hydrogen atom or a hydrocarbon grouphaving a carbon number of 1 to 10 and at least two members out of fourR^(1b) may combine to form a ring together with Q^(1b) and Q^(2b); m^(b)is 0 or 1 and when m^(b) is 0, Q^(1b) is bonded directly to theconjugated 5-membered ring including R^(2b) and R^(3b); and each ofR^(2b), R^(3b) and R^(4b) independently represents a hydrogen atom, ahalogen atom, a hydrocarbon group having a carbon number of 1 to 20, asilicon-containing hydrocarbon group containing from 1 to 6 silicons andhaving a carbon number of 1 to 18, a halogen-containing hydrocarbongroup having a carbon number of 1 to 20, a hydrocarbon group containingan oxygen atom or a sulfur atom and having a carbon number of 1 to 40,or a silyl group substituted with a hydrocarbon group having a carbonnumber of 1 to 40 and out of R^(2b), R^(3b) and R^(4b), only either onepair of adjacent R^(3b) and R^(3b) and adjacent R^(2b) and R^(3b) mayform a ring together with the carbon atoms to which the pair is bonded].

Component (A-2b): a metallocene compound represented by the followingformula (2b):

[in formula (2b), M^(2b) represents any one transition metal of Ti, Zrand Hf; each of X^(11b) and X^(12b) independently represents a hydrogenatom, a halogen atom, a hydrocarbon group having a carbon number of 1 to20, a hydrocarbon group containing an oxygen atom or a nitrogen atom andhaving a carbon number of 1 to 20, a hydrocarbon group-substituted aminogroup having a carbon number of 1 to 20, or an alkoxy group having acarbon number of 1 to 20; Q^(11b) represents a carbon atom, a siliconatom or a germanium atom; each R^(1b) independently represents ahydrogen atom or a hydrocarbon group having a carbon number of 1 to 10and two R^(11b) may combine with each other to form a ring together withQ^(11b); each of R^(12b), R^(14b) and R^(15b) independently representsan atom or a group selected from a hydrogen atom, a halogen atom, ahydrocarbon group having a carbon number of 1 to 20, asilicon-containing hydrocarbon group containing from 1 to 6 silicons andhaving a carbon number of 1 to 18, a halogen-containing hydrocarbongroup having a carbon number of 1 to 20, a hydrocarbon group containingan oxygen atom or a sulfur atom and having a carbon number of 1 to 40,and a silyl group substituted with a hydrocarbon group having a carbonnumber of 1 to 40, provided that at least one member is not a hydrogenatom; each R^(13b), independently represents a hydrocarbon group havinga carbon number of 1 to 20, a silicon-containing hydrocarbon groupcontaining from 1 to 6 silicons and having a carbon number of 1 to 18, ahalogen-containing hydrocarbon group having a carbon number of 1 to 20,a hydrocarbon group containing an oxygen atom or a sulfur atom andhaving a carbon number of 1 to 40, or a silyl group substituted with ahydrocarbon group having a carbon number of 1 to 40; and out of R^(12b),R^(13b), R^(14b) and R^(15b), any only one pair of adjacent R^(12b) andR^(12b), adjacent R^(13b) and R^(13b) and adjacent R^(12b) and R^(13b)and any only one pair of adjacent R^(14b) and R^(14b), adjacent R^(15b)and R^(15b) and adjacent R^(14b) and R^(15b) may form a ring togetherwith the carbon atoms to which the pair is bonded].

The components (A-1b) and (A-2b) (hereinafter, both are sometimescollectively referred to as component (Ab) or simply as Ab) arespecifically described below.

IV-1(1). Component (A-1b)

The olefin polymerization catalyst component of the present invention ischaracterized by containing a metallocene compound represented byformula (1b) as the component (A-1b).

In formula (1b), M^(1b) of the metallocene compound represents Ti, Zr orHf, preferably represents Zr or Hf, more preferably represents Zr.

Each of X^(1b) and X^(2b) specifically includes, for example, a hydrogenatom, a chlorine atom, a bromine atom, an iodine atom, a methyl group,an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group,an i-butyl group, a tert-butyl group, an n-pentyl group, a neopentylgroup, a cyclopentyl group, an n-hexyl group, a cyclohexyl group, aphenyl group, a benzyl group, a methoxymethyl group, an ethoxymethylgroup, an n-propoxymethyl group, an i-propoxymethyl group, ann-butoxymethyl group, an i-butoxymethyl group, a tert-butoxymethylgroup, a methoxyethyl group, an ethoxyethyl group, an acetyl group, a1-oxopropyl group, a 1-oxo-n-butyl group, a 2-methyl-1-oxopropyl group,a 2,2-dimethyl-1-oxo-propyl group, a phenylacetyl group, adiphenylacetyl group, a benzoyl group, a 2-methoxyphenyl group, a3-methoxyphenyl group, a 4-methoxyphenyl group, a 2-furyl group, a2-tetrahydrofuryl group, a dimethylaminomethyl group, adiethylaminomethyl group, a di-i-propylaminomethyl group, abis(dimethylamino)methyl group, a bis(di-i-propylamino)methyl group, a(dimethylamino)(phenyl)methyl group, a methylimino group, an ethyliminogroup, a 1-(methylimino)ethyl group, a 1-(phenylimino)ethyl group, a1-[(phenylmethyl)imino]ethyl group, an ethoxy group, an n-propoxy group,an i-propoxy group, an n-butoxy group, an i-butoxy group, a tert-butoxygroup, a phenoxy group, a dimethylamino group, a diethylamino group, adi-n-propylamino group, a di-i-propylamino group, a di-n-butylaminogroup, a di-i-butylamino group, a di-tert-butylamino group, and adiphenylamino group.

Specific preferred examples of X^(1b) and X^(2b) include a chlorineatom, a bromine atom, a methyl group, an n-butyl group, an i-butylgroup, a methoxy group, an ethoxy group, an i-propoxy group, an n-butoxygroup, a phenoxy group, a dimethylamino group, and a di-i-propylaminogroup. Among these specific examples, a chlorine atom, a methyl groupand a dimethylamino group are more preferred.

Each of Q^(1b) and Q^(2b) independently represents a carbon atom, asilicon atom or a germanium atom and is preferably a carbon atom or asilicon atom.

Each R^(1b) independently includes, for example, a hydrogen atom, amethyl group, an ethyl group, an n-propyl group, an i-propyl group, ann-butyl group, an i-butyl group, a tert-butyl group, an n-pentyl group,a neopentyl group, a cyclopentyl group, an n-hexyl group, a cyclohexylgroup, and a phenyl group. In the case where at least two R^(1b) arecombined to form a ring together with Q^(1b) and Q^(2b), examplesinclude a cyclobutylidene group, a cyclopentylidene group, acyclohexylidene group, a silacyclobutyl group, a silacyclopentyl group,and a silacyclohexyl group.

When Q^(1b) or/and Q^(2b) are a carbon atom, specific preferred examplesof R^(1b) include a hydrogen atom, a methyl group, an ethyl group, aphenyl group and a cyclobutylidene group, and when Q^(1b) or/and Q^(2b)are a silicon atom, specific preferred examples include a methyl group,an ethyl group, a phenyl group and a silacyclobutyl group.

Each of R^(2b), R^(3b) and R^(4b) specifically includes, for example, ahydrogen atom, a chlorine atom, a bromine atom, an iodine atom, a methylgroup, an ethyl group, an n-propyl group, an i-propyl group, an n-butylgroup, an i-butyl group, a tert-butyl group, an n-pentyl group, aneopentyl group, a cyclopentyl group, an n-hexyl group, a cyclohexylgroup, a phenyl group, a benzyl group, a 2-methylphenyl group, a3-methylphenyl group, a 4-methylphenyl group, a 3,5-dimethylphenylgroup, a 4-tert-butylphenyl group, a 3,5-di-tert-butylphenyl group, abis(trimethylsilyl)methyl group, a bis(tert-butyldimethylsilyl)methylgroup, a bromomethyl group, a chloromethyl group, a 2-chloroethyl group,a 2-bromoethyl group, a 2-bromopropyl group, a 3-bromopropyl group, a2-bromocyclopentyl group, a 2,3-dibromocyclopentyl group, a2-bromo-3-iodocyclopentyl group, a 2,3-dibromocyclohexyl group, a2-chloro-3-iodocyclohexyl group, a 2-chlorophenyl group, a4-chlorophenyl group, a 2,3,4,5,6-pentafluorophenyl group, a4-trifluoromethylphenyl group, a furyl group, a tetrahydrofuryl group, a2-methylfuryl group, a trimethylsilyl group, a tri-tert-butylsilylgroup, a di-tert-butylmethylsilyl group, a tert-butyldimethylsilylgroup, a triphenylsilyl group, a diphenylmethylsilyl group, aphenyldimethylsilyl group, a furyl group, a tetrahydrofuryl group, a2-methylfuryl group, and a 2-(trimethyl)silylfuryl group.

Out of R^(2b), R^(3b) and R^(4b), any one or more members are preferablya hydrocarbon group having a carbon number of 1 to 20, asilicon-containing hydrocarbon group containing from 1 to 6 silicons andhaving a carbon number of 1 to 18, a halogen-containing hydrocarbongroup having a carbon number of 1 to 20, a hydrocarbon group containingan oxygen atom and having a carbon number of 1 to 20, or a hydrocarbongroup-substituted silyl group having a carbon number of 1 to 20, becausethe polymerization activity is particularly increased.

Specific preferred examples of R^(2b), R^(3b) and R^(4b) include ahydrogen atom, a methyl group, an ethyl group, an n-propyl group, ani-propyl group, an n-butyl group, a tert-butyl group, an n-pentyl group,an n-hexyl group, a cyclohexyl group, a phenyl group, a 2-methylfurylgroup, and a trimethylsilyl group. Among these specific examples, ahydrogen atom, a methyl group, an n-butyl group, a tert-butyl group, aphenyl group and a trimethylsilyl group are more preferred, and ahydrogen atom, a methyl group, a tert-butyl group and a phenyl group arestill more preferred.

Specific examples of the condensed cyclopentadienyl structure formed byadjacent two R^(3b) and a cyclopentadienyl moiety to which both R^(3b)are bonded, include the following partial structures (I) to (VI), andspecific examples of the condensed cyclopentadienyl structure formed byadjacent R^(3b) and R^(2b) and a cyclopentadienyl moiety to which theseR^(3b) and R^(2b) are bonded, are the same.

Among these specific examples, (I), (II) and (VI) are preferred. Also,R^(4b) may be substituted on these partial structures (I) to (VI).

In formula (1b), m^(b) is 0 or 1 and when m^(b) is 0, Q^(1b) is bondeddirectly to the conjugated 5-membered ring including R^(2b) and R^(3b).

As the olefin polymerization catalyst component according to the presentinvention, the metallocene compound of the component (A-1b) ispreferably a compound represented by the following formula (3b):

[in formula (3b), M^(1b) represents any one transition metal of Ti, Zrand Hf; each of X^(1b) and X^(2b) independently represents a hydrogenatom, a halogen atom, a hydrocarbon group having a carbon number of 1 to20, a hydrocarbon group containing an oxygen atom or a nitrogen atom andhaving a carbon number of 1 to 20, a hydrocarbon group-substituted aminogroup having a carbon number of 1 to 20, or an alkoxy group having acarbon number of 1 to 20; each of Q^(1b) and Q^(2b) independentlyrepresents a carbon atom, a silicon atom or a germanium atom; eachR^(1b) independently represents a hydrogen atom or a hydrocarbon grouphaving a carbon number of 1 to 10 and at least two members out of fourR^(1b) may combine to form a ring together with Q^(1b) and Q^(2b); m^(b)is 0 or 1 and when m^(b) is 0. Q^(1b) is bonded directly to theconjugated 5-membered ring including R^(2b) and R^(3b); and each ofR^(2b), R^(3b) and R^(4b) independently represents a hydrogen atom, ahalogen atom, a hydrocarbon group having a carbon number of 1 to 20, asilicon-containing hydrocarbon group containing from 1 to 6 silicons andhaving a carbon number of 1 to 18, a halogen-containing hydrocarbongroup having a carbon number of 1 to 20, a hydrocarbon group containingan oxygen atom or a sulfur atom and having a carbon number of 1 to 40,or a silyl group substituted with a hydrocarbon group having a carbonnumber of 1 to 40 and out of R^(2b), R^(3b) and R^(4b), only either onepair of adjacent R^(3b) and R^(3b) and adjacent R^(2b) and R^(3b) mayform a ring together with the carbon atoms to which the pair is bonded].

In formula (3b), detailed definitions of M^(1b), X^(1b), X^(2b), Q^(1b),Q^(2b), R^(1b), R^(2b), R^(3b) and R^(4b) follow the definitions in thedescription of formula (1b) above.

In formula (3b), particularly when R^(3b) is a hydrogen atom, R^(2b) ispreferably a hydrogen atom or a hydrocarbon group having a carbon numberof 1 to 6 and while one of two R^(4b) is a hydrogen atom, the remainingone is preferably a hydrogen atom, a hydrocarbon group having a carbonnumber of 1 to 20, a silicon-containing hydrocarbon group containingfrom 1 to 6 silicons and having a carbon number of 1 to 18, ahalogen-containing hydrocarbon group having a carbon number of 1 to 20,a hydrocarbon group containing an oxygen atom or a sulfur atom andhaving a carbon number of 1 to 40, or a silyl group substituted with ahydrocarbon group having a carbon number of 1 to 40, specifically, theremaining one R^(4b) is preferably a hydrogen atom, a methyl group, anethyl group, an n-propyl group, an i-propyl group, an n-butyl group, ani-butyl group, a tert-butyl group, an n-pentyl group, a neopentyl group,a cyclopentyl group, an n-hexyl group, a cyclohexyl group, a phenylgroup, a benzyl group, a 2-methylphenyl group, a 3-methylphenyl group, a4-methylphenyl group, a 3,5-dimethylphenyl group, a 4-tert-butylphenylgroup, a 3,5-di-tert-butylphenyl group, a bis(trimethylsilyl)methylgroup, a bis(tert-butyldimethylsilyl)methyl group, a bromomethyl group,a chloromethyl group, a 2-chloroethyl group, a 2-bromoethyl group, a2-bromopropyl group, a 3-bromopropyl group, a 2-bromocyclopentyl group,a 2,3-dibromocyclopentyl group, a 2-bromo-3-iodocyclopentyl group, a2,3-dibromocyclohexyl group, a 2-chloro-3-iodocyclohexyl group, a2-chlorophenyl group, a 4-chlorophenyl group, a2,3,4,5,6-pentafluorophenyl group, a 4-trifluoromethylphenyl group, afuryl group, a tetrahydrofuryl group, a 2-methylfuryl group, atrimethylsilyl group, a tri-tert-butylsilyl group, adi-tert-butylmethylsilyl group, a tert-butyldimethylsilyl group, atriphenylsilyl group, a diphenylmethylsilyl group, a phenyldimethylsilylgroup, a furyl group, a tetrahydrofuryl group, a 2-methylfuryl group, a2-(trimethyl)silylfuryl group or the like: and R^(2b) is more preferablya hydrogen atom and while one of two R⁴ is a hydrogen atom, theremaining one is more preferably a hydrogen atom, a hydrocarbon grouphaving a carbon number of 1 to 20, or a silicon-containing hydrocarbongroup containing from 1 to 6 silicons and having a carbon number of 1 to18, specifically, the remaining one R^(4b) is more preferably a hydrogenatom, a methyl group, an ethyl group, an n-propyl group, an i-propylgroup, an n-butyl group, an i-butyl group, a tert-butyl group, ann-pentyl group, a neopentyl group, a cyclopentyl group, an n-hexylgroup, a cyclohexyl group, a phenyl group, a benzyl group, a2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a3,5-dimethylphenyl group, a 4-tert-butylphenyl group, a3,5-di-tert-butylphenyl group, a bis(trimethylsilyl)methyl group, abis(tert-butyldimethylsilyl)methyl group, a trimethylsilyl group, atri-tert-butylsilyl group, a di-tert-butylmethylsilyl group, atert-butyldimethylsilyl group, a triphenylsilyl group, adiphenylmethylsilyl group, a phenyldimethylsilyl group or the like. Theremaining one R^(1b) is specifically, still more preferably a hydrogenatom, a methyl group, an ethyl group, an n-propyl group, an i-propylgroup, an n-butyl group, an i-butyl group, a tert-butyl group, a phenylgroup, a trimethylsilyl group or a triphenylsilyl group, and theremaining one R^(4b), is specifically, yet still more preferably ahydrogen atom, an n-butyl group, an i-butyl group, a tert-butyl group, aphenyl group, a trimethylsilyl group or a triphenylsilyl group.

As the olefin polymerization catalyst component according to the presentinvention, the metallocene compound of the component (A-1b) is morepreferably a compound represented by the following formula (4b):

[in formula (4b), M^(1b) represents any one transition metal of Ti, Zrand Hf; each of X^(1b) and X^(2b) independently represents a hydrogenatom, a halogen atom, a hydrocarbon group having a carbon number of 1 to20, a hydrocarbon group containing an oxygen atom or a nitrogen atom andhaving a carbon number of 1 to 20, a hydrocarbon group-substituted aminogroup having a carbon number of 1 to 20, or an alkoxy group having acarbon number of 1 to 20; each of Q^(1b) and Q^(2b) independentlyrepresents a carbon atom, a silicon atom or a germanium atom; eachR^(1b) independently represents a hydrogen atom or a hydrocarbon grouphaving a carbon number of 1 to 10 and at least two members out of fourR^(1b) may combine to form a ring together with Q^(1b) and Q^(2b); m^(b)is 0 or 1 and when m^(b) is 0. Q^(1b) is bonded directly to theconjugated 5-membered ring including R^(2b), R^(5b) and R^(6b); and eachof R^(2b) and R^(4b) independently represents a hydrogen atom, a halogenatom, a hydrocarbon group having a carbon number of 1 to 20, asilicon-containing hydrocarbon group containing from 1 to 6 silicons andhaving a carbon number of 1 to 18, a halogen-containing hydrocarbongroup having a carbon number of 1 to 20, a hydrocarbon group containingan oxygen atom or a sulfur atom and having a carbon number of 1 to 40,or a silyl group substituted with a hydrocarbon group having a carbonnumber of 1 to 40 and R^(1b) does not form a ring together with thecarbon atom to which R^(4b) is bonded; R^(5b) represents a saturated orunsaturated divalent hydrocarbon group having a carbon number of 4 or 5for forming a condensed ring with the 5-membered ring to which R^(5b) isbonded; R^(6b) is an atom or a group bonded to a carbon atom of R^(5b)and each independently represents a hydrogen atom, a halogen atom, ahydrocarbon group having a carbon number of 1 to 20, asilicon-containing hydrocarbon group containing from 1 to 6 silicons andhaving a carbon number of 1 to 18, a halogen-containing hydrocarbongroup having a carbon number of 1 to 20, a hydrocarbon group containingan oxygen atom and having a carbon number of 1 to 20, or a hydrocarbongroup-substituted silyl group having a carbon number of 1 to 20; andn^(b) represents an integer of 0 to 10 and when n^(b) is 2 or more, atleast two R^(6b) may form a ring together with the carbon atoms to whichR^(6b) are bonded].

In formula (4b), detailed definitions of M^(1b), X^(1b), X^(2b), Q^(1b),Q^(2b), R^(1b), R^(2b) and R^(4b) follow the definitions in thedescription of formula (1b) above. Specific examples of the condensedcyclopentadienyl structure formed by R^(5b) and a cyclopentadienylmoiety to which R^(5b) is bonded, include the partial structures (I) to(VI). Among these specific examples, (I), (III) and (VI) are preferred.Also, R^(6′) may be substituted on these partial structures (I) to (VI).

The substituent R^(6b) includes, in addition to a hydrogen atom, forexample, a chlorine atom, a bromine atom, an iodine atom, a methylgroup, an ethyl group, an n-propyl group, an i-propyl group, an n-butylgroup, an i-butyl group, a tert-butyl group, an n-pentyl group, aneopentyl group, a cyclopentyl group, an n-hexyl group, a cyclohexylgroup, a phenyl group, a benzyl group, a 2-methylphenyl group, a3-methylphenyl group, a 4-methylphenyl group, a 4-tert-butylphenylgroup, a 3,5-dimethylphenyl group, a 3,5-di-tert-butylphenyl group, anaphthyl group, an anthracenyl group, a bis(trimethylsilyl)methyl group,a bis(tert-butyldimethylsilyl)methyl group, a bromomethyl group, achloromethyl group, a 2-chloroethyl group, a 2-bromoethyl group, a2-bromopropyl group, a 3-bromopropyl group, a 2-bromocyclopentyl group,a 2,3-dibromocyclopentyl group, a 2-bromo-3-iodocyclopentyl group, a2,3-dibromocyclohexyl group, a 2-chloro-3-iodocyclohexyl group, a2-chlorophenyl group, a 4-chlorophenyl group, a2,3,4,5,6-pentafluorophenyl group, a 2,6-dichloro-4-trimethylsilylphenylgroup, a trimethylsilyl group, a tri-tert-butylsilyl group, adi-tert-butylmethylsilyl group, a tert-butyldimethylsilyl group, atriphenylsilyl group, a diphenylmethylsilyl group, a phenyldimethylsilylgroup, a furyl group, a tetrahydrofuryl group, a 2-methylfuryl group,and a 2-(trimethyl)silylfuryl group. R^(6b) may form a ring togetherwith the carbon atom to which R^(6b) is bonded. Also, in formula (4b),particularly when R^(2b) is a hydrogen atom, all of two R^(4b) andR^(6b) are preferably a hydrogen atom or at least any one of two R^(4b)and R^(6b) is preferably a hydrocarbon group having a carbon number of 1to 20, a silicon-containing hydrocarbon group containing from 1 to 6silicons and having a carbon number of 1 to 18, a halogen-containinghydrocarbon group having a carbon number of 1 to 20, a hydrocarbon groupcontaining an oxygen atom or a sulfur atom and having a carbon number of1 to 40, or a silyl group substituted with a hydrocarbon group having acarbon number of 1 to 40, specifically, at least any one is preferably amethyl group, an ethyl group, an n-propyl group, an i-propyl group, ann-butyl group, an i-butyl group, a tert-butyl group, an n-pentyl group,a neopentyl group, a cyclopentyl group, an n-hexyl group, a cyclohexylgroup, a phenyl group, a benzyl group, a 2-methylphenyl group, a3-methylphenyl group, a 4-methylphenyl group, a 3,5-dimethylphenylgroup, a 4-tert-butylphenyl group, a 3,5-di-tert-butylphenyl group, abis(trimethylsilyl)methyl group, a bis(tert-butyldimethylsilyl)methylgroup, a bromomethyl group, a chloromethyl group, a 2-chloroethyl group,a 2-bromoethyl group, a 2-bromopropyl group, a 3-bromopropyl group, a2-bromocyclopentyl group, a 2,3-dibromocyclopentyl group, a2-bromo-3-iodocyclopentyl group, a 2,3-dibromocyclohexyl group, a2-chloro-3-iodocyclohexyl group, a 2-chlorophenyl group, a4-chlorophenyl group, a 2,3,4,5,6-pentafluorophenyl group, a4-trifluoromethylphenyl group, a furyl group, a tetrahydrofuryl group, a2-methylfuryl group, a trimethylsilyl group, a tri-tert-butylsilylgroup, a di-tert-butylmethylsilyl group, a tert-butyldimethylsilylgroup, a triphenylsilyl group, a diphenylmethylsilyl group, aphenyldimethylsilyl group, a furyl group, a tetrahydrofuryl group, a2-methylfuryl group, a 2-(trimethyl)silylfuryl group or the like. Inanother preferred embodiment when R^(2b) in formula (4b) is a hydrogenatom, while either one of two R^(4b) is a hydrogen atom, the remainingone is preferably a hydrocarbon group having a carbon number of 1 to 20,a silicon-containing hydrocarbon group containing from 1 to 6 siliconsand having a carbon number of 1 to 18, a halogen-containing hydrocarbongroup having a carbon number of 1 to 20, a hydrocarbon group containingan oxygen atom or a sulfur atom and having a carbon number of 1 to 40,or a silyl group substituted with a hydrocarbon group having a carbonnumber of 1 to 40, specifically, the remaining one R^(4b) is preferablya methyl group, an ethyl group, an n-propyl group, an i-propyl group, ann-butyl group, an i-butyl group, a tert-butyl group, an n-pentyl group,a neopentyl group, a cyclopentyl group, an n-hexyl group, a cyclohexylgroup, a phenyl group, a benzyl group, a 2-methylphenyl group, a3-methylphenyl group, a 4-methylphenyl group, a 3,5-dimethylphenylgroup, a 4-tert-butylphenyl group, a 3,5-di-tert-butylphenyl group, abis(trimethylsilyl)methyl group, a bis(tert-butyldimethylsilyl)methylgroup, a bromomethyl group, a chloromethyl group, a 2-chloroethyl group,a 2-bromoethyl group, a 2-bromopropyl group, a 3-bromopropyl group, a2-bromocyclopentyl group, a 2,3-dibromocyclopentyl group, a2-bromo-3-iodocyclopentyl group, a 2,3-dibromocyclohexyl group, a2-chloro-3-iodocyclohexyl group, a 2-chlorophenyl group, a4-chlorophenyl group, a 2,3,4,5,6-pentafluorophenyl group, a4-trifluoromethylphenyl group, a furyl group, a tetrahydrofuryl group, a2-methylfuryl group, a trimethylsilyl group, a tri-tert-butylsilylgroup, a di-tert-butylmethylsilyl group, a tert-butyldimethylsilylgroup, a triphenylsilyl group, a diphenylmethylsilyl group, aphenyldimethylsilyl group, a furyl group, a tetrahydrofuryl group, a2-methylfuryl group, a 2-(trimethyl)silylfuryl group or the like; andwhile either one of two R^(4b) is a hydrogen atom, the remaining one ismore preferably a hydrocarbon group having a carbon number of 1 to 20 ora silicon-containing hydrocarbon group containing from 1 to 6 siliconsand having a carbon number of 1 to 18, specifically, the remaining oneR^(4b) is preferably a methyl group, an ethyl group, an n-propyl group,an i-propyl group, an n-butyl group, an i-butyl group, a tert-butylgroup, an n-pentyl group, a neopentyl group, a cyclopentyl group, ann-hexyl group, a cyclohexyl group, a phenyl group, a benzyl group, a2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a3,5-dimethylphenyl group, a 4-tert-butylphenyl group, a3,5-di-tert-butylphenyl group, a bis(trimethylsilyl)methyl group, abis(tert-butyldimethylsilyl)methyl group, a trimethylsilyl group, atri-tert-butylsilyl group, a di-tert-butylmethylsilyl group, atert-butyldimethylsilyl group, a triphenylsilyl group, adiphenylmethylsilyl group, a phenyldimethylsilyl group or the like. Theremaining one R^(4b) is specifically, still more preferably a methylgroup, an ethyl group, an n-propyl group, an i-propyl group, an n-butylgroup, an i-butyl group, a tert-butyl group, a phenyl group, atrimethylsilyl group or a triphenylsilyl group; and the remaining oneR^(4b) is specifically, yet still more preferably an n-butyl group, ani-butyl group, a tert-butyl group, a phenyl group, a trimethylsilylgroup or a triphenylsilyl group. Furthermore, in formula (4b),particularly when R^(4b) is a hydrogen atom, each of R^(2b) and R^(6b)is preferably any one of a hydrogen atom, a hydrocarbon group having acarbon number of 1 to 20, a silicon-containing hydrocarbon groupcontaining from 1 to 6 silicons and having a carbon number of 1 to 18, ahalogen-containing hydrocarbon group having a carbon number of 1 to 20,a hydrocarbon group containing an oxygen atom or a sulfur atom andhaving a carbon number of 1 to 40, and a silyl group substituted with ahydrocarbon group having a carbon number of 1 to 40, specifically, eachof R^(2b) and R^(6b) is preferably any one of a hydrogen atom, a methylgroup, an ethyl group, an n-propyl group, an i-propyl group, an n-butylgroup, an i-butyl group, a tert-butyl group, an n-pentyl group, aneopentyl group, a cyclopentyl group, an n-hexyl group, a cyclohexylgroup, a phenyl group, a benzyl group, a 2-methylphenyl group, a3-methylphenyl group, a 4-methylphenyl group, a 3,5-dimethylphenylgroup, a 4-tert-butylphenyl group, a 3,5-di-tert-butylphenyl group, abis(trimethylsilyl)methyl group, a bis(tert-butyldimethylsilyl)methylgroup, a bromomethyl group, a chloromethyl group, a 2-chloroethyl group,a 2-bromoethyl group, a 2-bromopropyl group, a 3-bromopropyl group, a2-bromocyclopentyl group, a 2,3-dibromocyclopentyl group, a2-bromo-3-iodocyclopentyl group, a 2,3-dibromocyclohexyl group, a2-chloro-3-iodocyclohexyl group, a 2-chlorophenyl group, a4-chlorophenyl group, a 2,3,4,5,6-pentafluorophenyl group, a4-trifluoromethylphenyl group, a furyl group, a tetrahydrofuryl group, a2-methylfuryl group, a trimethylsilyl group, a tri-tert-butylsilylgroup, a di-tert-butylmethylsilyl group, a tert-butyldimethylsilylgroup, a triphenylsilyl group, a diphenylmethylsilyl group, aphenyldimethylsilyl group, a furyl group, a tetrahydrofuryl group, a2-methylfuryl group, a 2-(trimethyl)silylfuryl group and the like; andeach of R^(2b) and R^(6b) is more preferably a hydrogen atom, ahydrocarbon group having a carbon number of 1 to 20, or asilicon-containing hydrocarbon group containing from 1 to 6 silicons andhaving a carbon number of 1 to 18, specifically, each of R^(2b) andR^(6b) is more preferably a hydrogen atom, a methyl group, an ethylgroup, an n-propyl group, an i-propyl group, an n-butyl group, ani-butyl group, a tert-butyl group, an n-pentyl group, a neopentyl group,a cyclopentyl group, an n-hexyl group, a cyclohexyl group, a phenylgroup, a benzyl group, a 2-methylphenyl group, a 3-methylphenyl group, a4-methylphenyl group, a 3,5-dimethylphenyl group, a 4-tert-butylphenylgroup, a 3,5-di-tert-butylphenyl group, a bis(trimethylsilyl)methylgroup, a bis(tert-butyldimethylsilyl)methyl group, a trimethylsilylgroup, a tri-tert-butylsilyl group, a di-tert-butylmethylsilyl group, atert-butyldimethylsilyl group, a triphenylsilyl group, adiphenylmethylsilyl group, a phenyldimethylsilyl group or the like. Eachof R^(2b) and R^(6b) is specifically, still more preferably a hydrogenatom, a methyl group, an ethyl group, an n-propyl group, an i-propylgroup, an n-butyl group, an i-butyl group, a tert-butyl group, a phenylgroup, a trimethylsilyl group, or a triphenylsilyl group, and each ofR^(2b) and R^(6b) is specifically, yet still more preferably a hydrogenatom, an n-butyl group, an i-butyl group, a tert-butyl group, a phenylgroup, a trimethylsilyl group or a triphenylsilyl group.

As the olefin polymerization catalyst component according to the presentinvention, the metallocene compound of the component (A-1b) is stillmore preferably a compound represented by the following formula (5b):

[in formula (5b), M^(1b) represents any one transition metal of Ti, Zrand Hf; each of X^(1b) and X^(2b) independently represents a hydrogenatom, a halogen atom, a hydrocarbon group having a carbon number of 1 to20, a hydrocarbon group containing an oxygen atom or a nitrogen atom andhaving a carbon number of 1 to 20, a hydrocarbon group-substituted aminogroup having a carbon number of 1 to 20, or an alkoxy group having acarbon number of 1 to 20: Q^(1b) represents a carbon atom, a siliconatom or a germanium atom; each R^(1b) independently represents ahydrogen atom or a hydrocarbon group having a carbon number of 1 to 10and two R^(1b) may combine with each other to form a ring together withQ^(1b); and each of R^(2b), R^(4b) and R^(6b) independently represents ahydrogen atom, a halogen atom, a hydrocarbon group having a carbonnumber of 1 to 20, a silicon-containing hydrocarbon group containingfrom 1 to 6 silicons and having a carbon number of 1 to 18, ahalogen-containing hydrocarbon group having a carbon number of 1 to 20,a hydrocarbon group containing an oxygen atom or a sulfur atom andhaving a carbon number of 1 to 40, or a silyl group substituted with ahydrocarbon group having a carbon number of 1 to 40 and R^(4b) does notform a ring together with the carbon atom to which R^(4b) is bonded; andR^(6b) may form a ring together with the carbon atoms to which R^(6b) isbonded].

In formula (5b), detailed definitions of M^(1b), X^(1b), X^(2b), Q^(1b),R^(1b), R^(2b), R^(4b) and R^(6b) follow the definitions in thedescription of formula (4b) above. The substituent R^(6b) is preferablya hydrogen atom, a methyl group, an ethyl group, an n-propyl group, ani-propyl group, an n-butyl group, an i-butyl group, a tert-butyl group,an n-pentyl group, a neopentyl group, a cyclopentyl group, an n-hexylgroup, a cyclohexyl group, a phenyl group, a benzyl group, a2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a4-tert-butylphenyl group, a 3,5-dimethylphenyl group, a3,5-di-tert-butylphenyl group, a bis(trimethylsilyl)methyl group, abis(tert-butyldimethylsilyl)methyl group, a trimethylsilyl group, atri-tert-butylsilyl group, a di-tert-butylmethylsilyl group, atert-butyldimethylsilyl group, a triphenylsilyl group, adiphenylmethylsilyl group, a phenyldimethylsilyl group, a furyl group, atetrahydrofuryl group, a 2-methylfuryl group or a2-(trimethyl)silylfuryl group, more preferably a hydrogen atom, a methylgroup, an ethyl group, an n-propyl group, an i-propyl group, an n-butylgroup, a tert-butyl group, an n-pentyl group, an n-hexyl group, acyclohexyl group or a phenyl group, still more preferably a hydrogenatom, a methyl group, an n-butyl group, a tert-butyl group, a phenylgroup or a trimethylsilyl group, yet still more preferably a hydrogenatom, a methyl group, a tert-butyl group or a phenyl group. In the casewhere the substituents R^(6b) form a ring together with the carbon atomto which the substituents are bonded, preferably, adjacent two R^(6b)form a 6-membered ring structure together with the carbon atoms to whichthese substituents are bonded; more preferably, both R^(6b) on the4-position and the 5-position combine to form a 6-membered ringstructure; and still more preferably, a benzindenyl ring structure isformed as a whole together with the indenyl ring to which thesubstituents are bonded.

In the olefin polymerization catalyst component of the presentinvention, specific examples of the metallocene compound as thecomponent (A-1b) of the olefin polymerization catalyst component areillustrated below, but the present invention is not limited thereto.Incidentally, the number indicating the position of each substituent onthe cyclopentadienyl ring, indenyl ring and azulenyl ring of metallocenecompounds recited as specific examples of the component (A-1b) and thelater-described (A-2b) is as shown in the following formulae.

(i) The metallocene compounds classified into a bridged Cp(Ind)Zr typeinclude, for example, those shown in Table b-1 below.

TABLE b-1 (i) Bridged Cp(Ind)Zr Type

No. A1 A2 A3  1b dimethylsilylene Cl Cl  2b dimethylsilylene Me Me  3bdimethylsilylene Ph Ph  4b isopropylidene Cl Cl  5b silacyclobutyl Cl Cl 6b silacyclopentyl Cl Cl  7b silacyclohexyl Cl Cl  8b cyclobutylideneCl Cl  9b cyclopentylidene Cl Cl 10b cyclohexylidene Cl Cl 11bdimethylgermirene Cl Cl

(ii) The metallocene compounds classified into a bridgedCp(3-substituted Ind)Zr type include, for example, those shown in Tablesb-2 and b-3 below.

TABLE b-2 (ii) Bridged Cp(3-Substituted Ind)Zr Type

No. A1 A2 A3 A4 A5 12b dimethylsilylene 3-methyl — chloride chloride C13b dimethylsilylene 3-methyl — methyl methyl C 14b isopropylidene3-methyl — chloride chloride A 15b dimethylsilylene 3-ethyl — chloridechloride B 16b isopropylidene 3-ethyl — chloride chloride A 17bdimethylsilylene 3-n-propyl — chloride chloride B 18b isopropylidene3-n-propyl — chloride chloride A 19b dimethylsilylene 3-i-propyl —chloride chloride B 20b isopropylidene 3-i-propyl — chloride chloride A21b dimethylsilylene 3-n-butyl — chloride chloride 22b isopropylidene3-n-butyl — chloride chloride 23b dimethylsilylene 3-tert-butyl —chloride chloride 24b cyclobutylidene 3-tert-butyl — chloride chloride25b dimethylsilylene 3-tert-butyl — methyl methyl 26b isopropylidene3-tert-butyl — chloride chloride 27b dimethylsilylene 3-n-pentyl —chloride chloride 28b dimethylsilylene 3-n-hexyl — chloride chloride 29bdimethylsilylene 3-cyclohexyl — chloride chloride B 30b dimethylsilylene3-phenyl — chloride chloride 31b dimethylsilylene 3-benzyl — chloridechloride B 32b dimethylsilylene 3-tolyl — chloride chloride 33bdimethylsilylene 3-trimethylsilyl — chloride chloride A 34bdimethylsilylene 3-chlorophenyl — chloride chloride A 35bdimethylsilylene 3-fluorophenyl — chloride chloride B 36bdimethylsilylene 3-(5-methyl-2-furyl) — chloride chloride C 37bdimethylsilylene — 4-methyl chloride chloride B 38b dimethylsilylene —5-methyl chloride chloride B 39b dimethylsilylene — 6-methyl chloridechloride C 40b dimethylsilylene 3-methyl 4-methyl chloride chloride 41bdimethylsilylene 3-tert-butyl 4-methyl chloride chloride C 42bdimethylsilylene — 4-phenyl chloride chloride C 43b dimethylsilylene —4-(4-methylphenyl) chloride chloride C 44b dimethylsilylene —4-(4-tert-butylphenyl) chloride chloride 45b dimethylgermirene 3-methyl— chloride chloride

TABLE b-3 (ii) Bridged Cp(3-substituted Ind)Zr Type (continued) No. A1A2 A3 A4 A5 46b dimethylgermirene 3-ethyl — chloride chloride 47bdimethylgermirene 3-i-propyl — chloride chloride 48b dimethylgermirene3-n-butyl — chloride chloride 49b dimethylgermirene 3-tert-butyl —chloride chloride 50b diethylsilylene — — chloride chloride C 51bdiethylsilylene 3-methyl — chloride chloride B 52b diethylsilylene3-ethyl — chloride chloride B 53b diethylsilylene 3-i-propyl — chloridechloride 54b diethylsilylene 3-n-butyl — chloride chloride 55bdiethylsilylene 3-tert-butyl — chloride chloride 56b di-n-butylsilylene— — chloride chloride C 57b di-n-butylsilylene 3-methyl — chloridechloride B 58b di-n-butylsilylene 3-ethyl — chloride chloride B 59bdi-n-butylsilylene 3-i-propyl — chloride chloride 60b di-n-butylsilylene3-n-butyl — chloride chloride 61b di-n-butylsilylene 3-tert-butyl —chloride chloride 62b diphenylsilylene — — chloride chloride 63bdiphenylmethylene — — chloride chloride C 64b diphenylsilylene 3-methyl— chloride chloride B 65b diphenylsilylene 3-ethyl — chloride chloride B66b diphenylsilylene 3-i-propyl — chloride chloride 67b diphenylsilylene3-n-butyl — chloride chloride 68b diphenylsilylene 3-tert-butyl —chloride chloride C 69b dimethylsilylene — benz[e] chloride chloride C70b dimethylsilylene — dibenzo chloride chloride 71b dimethylsilylene —azulenyl chloride chloride C 72b dimethylsilylene — 4-methylazulenylchloride chloride C 73b dimethylsilylene — 4-phenylazulenyl chloridechloride B 74b dimethylsilylene — 5,6-dimethyl chloride chloride C 75bdimethylsilylene — benz[f] chloride chloride 76b dimethylsilylene —6,7-dihydroindacenyl chloride chloride 77b dimethylsilylene —5,5,7,7-tetramethyl- chloride chloride 6,7-dihydroindacenyl 78bdimethylsilylene — 5,6,7,8-tetra- chloride chloride hydrobenz[f] 79bdimethylsilylene — 5,6,7,8-tetrahydro- chloride chloride5,5,8,8-tetramethyl- benz[f]

(iii) The metallocene compounds classified into a bridged (3-substitutedCp)(Ind)Zr type include, for example, those shown in Table b-4 below.

TABLE 20 [Table b-4] (iii) Bridged (3-Substituted Cp) (Ind) Zr Type

No. A1 A2 A3 A4 A5 80b dimethylsilylene 4-methyl — chloride chloride C81b dimethylsilylene 4-ethyl — chloride chloride C 82b dimethylsilylene4-i-propyl — chloride chloride C 83b dimethylsilylene 4-n-butyl —chloride chloride C 84b dimethylsilylene 4-i-butyl — chloride chloride C85b dimethylsilylene 4-tert-butyl — chloride chloride C 86bdimethylsilylene 4-tert-butyl — bromide bromide C 87b dimethylsilylene4-tert-butyl — methyl methyl C 88b dimethylsilylene 4-tert-butyl —phenyl phenyl C 89b dimethylsilylene 4-tert-butyl 4,5,6,7- chloridechloride C tetrahydro 90b dimethylsilylene 4-tert-butyl azulenylchloride chloride C 91b dimethylsilylene 4- — chloride chloride Ctrimethylsilyl 92b dimethylsilylene 4-(2- — chloride chloride Abromoethyl) 93b dimethylsilylene 4-(2- — chloride chloride C trimethyl-silylfuryl) 94b dimethylsilylene 4-phenyl — chloride chloride C 95bdimethylsilylene 4-(4-methyl — chloride chloride C phenyl) 96bisopropylidene 4-tert-butyl — chloride chloride A 97b dimethyl-4-tert-butyl — chloride chloride germirene

(iv) The metallocene compounds classified into a bridged (4-substitutedCp)(3-substituted Ind)Zr type include, for example, those shown in Tableb-5 below.

TABLE 21 [Table b-5] (iv) Bridged (4-Substituted Cp) (3-Substituted Ind)Zr Type

No. A1 A2 A3 A4 A5 A6 98b dimethylsilylene 4-tert- 3-methyl — chloridechloride butyl 99b dimethylsilylene 4-tert- 3-tert- — chloride chloridebutyl butyl 100b dimethylsilylene 4-tert- 3-tert- — chloride chloridebutyl butyl 101b dimethylsilylene 4-tert- — 4-phenyl chloride chloridebutyl 102b dimethylsilylene 3,4- 3-tert- — chloride chloride dimethylbutyl 103b isopropylidene 4-tert- 3-n-butyl — chloride chloride butyl104b dimethylsilylene 4-tert- — 4- chloride chloride butyl phenyl-azulenyl

(v) The metallocene compounds classified into a bridged bisCpZr typeinclude, for example, those shown in Table b-6 below.

TABLE 22 [Table b-6] (v) Bridged bisCpZr Type

No. A1 A2 A3 105b dimethylsilylene chloride chloride 106bdimethylsilylene methyl methyl 107b dimethylsilylene phenyl phenyl 108bdimethylsilylene benzyl benzyl 109b isopropylidene chloride chloride110b silacyclobutyl chloride chloride 111b dimethylgermirene chloridechloride

(vi) The metallocene compounds classified into a bridgedCp(3-substituted Cp)Zr type include, for example, those shown in Tableb-7 below.

TABLE 23 [Table b-7] (vi) Bridged Cp (3-substituted Cp) Zr Type

No. A1 A2 A3 A4 112b dimethylsilylene 3-n-propyl chloride chloride C113b dimethylsilylene 3-tert-butyl chloride chloride C 114bdimethylsilylene 3-cyclohexyl chloride chloride C 115b dimethylsilylene3-biphenyl chloride chloride C 116b dimethylsilylene 3-(4-methylphenyl)chloride chloride C 117b dimethylsilylene 3-(5-methyl-2-furyl) chloridechloride C 118b dimethylsilylene 3-tert-butyl-4-methyl chloride chlorideB 119b dimethylsilylene 3-tert-butyl-4-ethyl chloride chloride B 120bisopropylidene 3-tert-butyl chloride chloride A 121b dimethylgermirene3-tert-butyl chloride chloride

(vii) The metallocene compounds classified into a bridgedbis(3-substituted Cp)Zr type include, for example, those shown in Tableb-8 below.

TABLE 24 [Table b-8] (vii) Bridged bis(3-substituted Cp)Zr Type

No. A1 A2 A3 A4 A5 122b dimethylsilyiene 3-tert-butyl 3-tert-butylchloride chloride 123b dimethylsilylene 3-tert-butyl 3-tert-butyl methylmethyl 124b dimethylsilylene 3-tert-butyl 3-tert-butyl phenyl phenyl125b isopropylidene 3-tert-butyl 3-tert-butyl chloride chloride 126bsilacyclobutyl 3-tert-butyl 3-tert-butyl chloride chloride 127bdimethylgermirene 3-tert-butyl 3-tert-butyl chloride chloride 128bdimethylsilylene 3-allyl 3-allyl chloride chloride 129b dimethylsilylene3-trimethylsilyl 3-trimethylsilyl chloride chloride 130bdimethylsilylene 3-ethyl-4-methyl 3-ethyl-4-methyl chloride chloride131b dimethylsilylene 3-tert-butyl-4- 3-tert-butyl-4- chloride chloridemethyl methyl 132b dimethylsilylene 3-(2-bromoethyl) 3-(2-bromoethyl)chloride chloride 133b dimethylsilylene 3-(4-chlorophenyl)3-(4-chlorophenyl) chloride chloride 134b dimethylsilylene 3-benzyl3-benzyl chloride chloride 135b dimethylsilylene 3-(5-methyl-2-3-(5-methyl-2- chloride chloride furyl) furyl) 136b dimethylsilylene3-tert-butyl 3-methyl chloride chloride 137b dimethylsilylene3-tert-butyl 4-tert-butyl chloride chloride 138b dimethylsilylene3-methyl 4-phenyl chloride chloride 139b dimethylsilylene 3, 4-dimethyl3-tert-butyl chloride chloride 140b dimethylsilylene 3,4-dimethyl3-(2-methylfuryl) chloride chloride 141b dimethylsilylene3-methyl-4-phenyl 3-tert-butyl-4- chloride chloride ethyl

The metallocene compound also includes, for example, compounds wherezirconium of the compounds above is replaced by titanium or hafnium.

Furthermore, in using these metallocene compounds as the component(A-1b), two or more thereof may be also used.

In specific compounds exemplified above, in terms of excellentperformance in both polymerization activity and moldability, preferredmetallocene compounds as the component (A-1b) are denoted by “A”, morepreferred compounds are denoted by “B”, and still more preferredcompounds are denoted by “C”.

Synthesis examples for the metallocene compound as the component (A-1b)according to the present invention are described below, but the presentinvention is not limited to these synthesis methods in particular.

For example, there are a method where an indene compound is lithiated,then reacted with a dichlorosilane compound and subsequently reactedwith cyclopentadienyl lithium to obtain a ligand and the obtained ligandis reacted with a tetrakis(alkylamido)zirconium and then withtrimethylsilyl chloride, and a method where the obtained ligand islithiated and subsequently reacted with zirconium tetrachloride.

IV-1(2). Component (A-2b) The olefin polymerization catalyst componentof the present invention is characterized by containing a metallocenecompound represented by formula (2b) as the component (A-2b).

In formula (2b), M^(2b) of the metallocene compound represents Ti, Zr orHf, preferably represents Zr or Hf, more preferably represents Zr.

Each of X^(11b) and X^(12b) specifically includes, for example, ahydrogen atom, a chlorine atom, a bromine atom, an iodine atom, a methylgroup, an ethyl group, an n-propyl group, an i-propyl group, an n-butylgroup, an i-butyl group, a tert-butyl group, an n-pentyl group, aneopentyl group, a cyclopentyl group, an n-hexyl group, a cyclohexylgroup, a phenyl group, a benzyl group, a methoxymethyl group, anethoxymethyl group, an n-propoxymethyl group, an i-propoxymethyl group,an n-butoxymethyl group, an i-butoxymethyl group, a tert-butoxymethylgroup, a methoxyethyl group, an ethoxyethyl group, an acetyl group, a1-oxopropyl group, a 1-oxo-n-butyl group, a 2-methyl-1-oxopropyl group,a 2,2-dimethyl-1-oxo-propyl group, a phenylacetyl group, adiphenylacetyl group, a benzoyl group, a 2-methoxyphenyl group, a3-methoxyphenyl group, a 4-methoxyphenyl group, a 2-furyl group, a2-tetrahydrofuryl group, a dimethylaminomethyl group, adiethylaminomethyl group, a di-i-propylaminomethyl group, abis(dimethylamino)methyl group, a bis(di-i-propylamino)methyl group, a(dimethylamino)(phenyl)methyl group, a methylimino group, an ethyliminogroup, a 1-(methylimino)ethyl group, a 1-(phenylimino)ethyl group, a1-[(phenynlmethyl)imino]ethyl group, an ethoxy group, an n-propoxygroup, an i-propoxy group, an n-butoxy group, an i-butoxy group, atert-butoxy group, a phenoxy group, a dimethylamino group, adiethylamino group, a di-n-propylamino group, a di-i-propylamino group,a di-n-butylamino group, a di-i-butylamino group, a di-tert-butylaminogroup, and a diphenylamino group.

Specific preferred examples of X^(11b) and X^(12b), each independently,include a chlorine atom, a bromine atom, a methyl group, an n-butylgroup, an i-butyl group, a methoxy group, an ethoxy group, an i-propoxygroup, an n-butoxy group, a phenoxy group, a dimethylamino group, and adi-i-propylamino group. Among these specific examples, a chlorine atom,a methyl group and a dimethylamino group are more preferred.

Q^(11b) represents a carbon atom, a silicon atom or a germanium atom andis preferably a carbon atom or a silicon atom.

Each R^(11b) independently includes, for example, a hydrogen atom, amethyl group, an ethyl group, an n-propyl group, an i-propyl group, ann-butyl group, an i-butyl group, a tert-butyl group, an n-pentyl group,a neopentyl group, a cyclopentyl group, an n-hexyl group, a cyclohexylgroup, and a phenyl group. In the case where R^(11b) forms a ringtogether with Q^(11b), examples include a cyclobutylidene group, acyclopentylidene group, a cyclohexylidene group, a silacyclobutyl group,a silacyclopentyl group, and a silacyclohexyl group.

When Q^(11b) is a carbon atom, specific preferred examples of R^(11b)include a hydrogen atom, a methyl group, an ethyl group, a phenyl groupand a cyclobutylidene group, and when Q^(11b) is a silicon atom,specific preferred examples include a methyl group, an ethyl group, aphenyl group and a silacyclobutyl group.

Each of R^(12b), R^(14b) and R^(15b) specifically includes an element ora group selected from, for example, a hydrogen atom, a chlorine atom, abromine atom, an iodine atom, a methyl group, an ethyl group, ann-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, atert-butyl group, an n-pentyl group, a neopentyl group, a cyclopentylgroup, an n-hexyl group, a cyclohexyl group, a phenyl group, a benzylgroup, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenylgroup, a 3,5-dimethylphenyl group, a 4-tert-butylphenyl group, a3,5-di-tert-butylphenyl group, a bis(trimethylsilyl)methyl group, abis(tert-butyldimethylsilyl)methyl group, a bromomethyl group, achloromethyl group, a 2-chloroethyl group, a 2-bromoethyl group, a2-bromopropyl group, a 3-bromopropyl group, a 2-bromocyclopentyl group,a 2,3-dibromocyclopentyl group, a 2-bromo-3-iodocyclopentyl group, a2,3-dibromocyclohexyl group, a 2-chloro-3-iodocyclohexyl group, a2-chlorophenyl group, a 4-chlorophenyl group, a2,3,4,5,6-pentafluorophenyl group, a 4-trifluoromethylphenyl group, atrimethylsilyl group, a tri-tert-butylsilyl group, adi-tert-butylmethylsilyl group, a tert-butyldimethylsilyl group, atriphenylsilyl group, a diphenylmethylsilyl group, a phenyldimethylsilylgroup, a furyl group, a tetrahydrofuryl group, a 2-methylfuryl group,and a 2-(trimethyl)silylfuryl group, provided that at least one memberthereof is not a hydrogen atom; specifically, each is preferably anelement or a group selected from a hydrogen atom, a methyl group, anethyl group, an n-propyl group, an i-propyl group, an n-butyl group, ani-butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group,a cyclohexyl group, a phenyl group, a trimethylsilyl group, a furylgroup, a 2-methylfuryl group and a 2-(trimethyl)silyl group, providedthat at least one member thereof is not a hydrogen atom; andspecifically, each is more preferably an element or a group selectedfrom a hydrogen atom, a methyl group, an n-butyl group, a tert-butylgroup, a phenyl group, a trimethylsilyl group, a 2-methylfuryl group anda 2-(trimethyl)silylfuryl group, provided that at least one memberthereof is not a hydrogen atom. The member that is not a hydrogen atomis preferably at least one member out of R^(12b) located on the2-position of the cyclopentadienyl ring, R^(14b) located on the same2-position and two R^(15b); the member that is not a hydrogen atom ismore preferably at least one member out of R^(12b) located on the2-position of the cyclopentadienyl ring and two R^(15′); and the memberthat is not a hydrogen atom is still more preferably at least one memberout of R^(12b) located on the 2-position of the cyclopentadienyl ringand R^(15b) located on the same 2-position.

Each R^(13b) independently includes, for example, a methyl group, anethyl group, an n-propyl group, an i-propyl group, an n-butyl group, ani-butyl group, a tert-butyl group, an n-pentyl group, a neopentyl group,a cyclopentyl group, an n-hexyl group, a cyclohexyl group, a phenylgroup, a benzyl group, a 2-methylphenyl group, a 3-methylphenyl group, a4-methylphenyl group, a 3,5-dimethylphenyl group, a 4-tert-butylphenylgroup, a 3,5-di-tert-butylphenyl group, a bis(trimethylsilyl)methylgroup, a bis(tert-butyldimethylsilyl)methyl group, a bromomethyl group,a chloromethyl group, a 2-chloroethyl group, a 2-bromoethyl group, a2-bromopropyl group, a 3-bromopropyl group, a 2-bromocyclopentyl group,a 2,3-dibromocyclopentyl group, a 2-bromo-3-iodocyclopentyl group, a2,3-dibromocyclohexyl group, a 2-chloro-3-iodocyclohexyl group, a2-chlorophenyl group, a 4-chlorophenyl group, a2,3,4,5,6-pentafluorophenyl group, a 4-trifluoromethylphenyl group, atrimethylsilyl group, a tri-tert-butylsilyl group, adi-tert-butylmethylsilyl group, a tert-butyldimethylsilyl group, atriphenylsilyl group, a diphenylmethylsilyl group, a phenyldimethylsilylgroup, a furyl group, a tetrahydrofuryl group, a 2-methylfuryl group,and a 2-(trimethyl)silylfuryl group; preferably, each is independently amethyl group, an ethyl group, an n-propyl group, an i-propyl group, ann-butyl group, an i-butyl group, a tert-butyl group, an n-pentyl group,an n-hexyl group, a cyclohexyl group, a phenyl group, a trimethylsilylgroup, a furyl group, a 2-methylfuryl group or a 2-(trimethyl)silylgroup; and more preferably, each is independently an element or a groupselected from a methyl group, an n-butyl group, a tert-butyl group, aphenyl group, a trimethylsilyl group, a 2-methylfuryl group and a2-(trimethyl)silylfuryl group.

In formula (2b), adjacent R^(12b) and R^(12b) may form a condensedcyclopentadienyl structure of the partial structure (I) to (VI)described in the component (A-1b), preferably a condensedcyclopentadienyl structure of (I), (III) or (VI), together with thecarbon atom on the cyclopentadienyl ring, to which those members arebonded, but in this case, the ring structure above is not formed betweenadjacent R^(13b) and R^(13b) and between adjacent R^(12b) and R^(13b).Similarly, adjacent R^(13b) and R^(13b) may form a condensedcyclopentadienyl structure of (I) to (VI), preferably a condensedcyclopentadienyl structure of (I), (III) or (VI), but in this case, thering structure above is not formed between adjacent R^(12b) and R^(12b)and between adjacent R^(12b) and R^(13b). Also, similarly, adjacentR^(13b) and R^(13b) may form a condensed cyclopentadienyl structure of(I) to (VI), preferably a condensed cyclopentadienyl structure of (I),(III) or (VI), but in this case, the ring structure above is not formedbetween adjacent R^(12b) and R^(12b) and between adjacent R^(12b) andR^(13b).

Furthermore, in formula (2b), adjacent R^(14b) and R^(14b) may form acondensed cyclopentadienyl structure of (I) to (VI), preferably acondensed cyclopentadienyl structure of (I), (III) or (VI), but in thiscase, the ring structure above is not formed between adjacent R^(15b)and R^(15b) and between adjacent R^(14b) and R^(15b). Similarly,adjacent R^(15b) and R^(15b) may form a condensed cyclopentadienylstructure of (I) to (VI), preferably a condensed cyclopentadienylstructure of (I), (III) or (VI), but in this case, the ring structureabove is not formed between adjacent R^(14b) and R^(14b) and betweenadjacent R^(14b) and R^(15b). Also, similarly, adjacent R^(14b) andR^(15b) may form a condensed cyclopentadienyl structure of (I) to (VI),preferably a condensed cyclopentadienyl structure of (I), (III) or (VI),but in this case, the ring structure above is not formed betweenadjacent R^(14b) and R^(14b) and between adjacent R^(15b) and R^(15b).

As the olefin polymerization catalyst component according to the presentinvention, the metallocene compound of the component (A-2b) ispreferably a compound represented by the following formula (6b):

[in formula (6b), M^(2b) represents any one transition metal of Ti, Zrand Hf; each of X^(11b) and X^(12b) independently represents a hydrogenatom, a halogen atom, a hydrocarbon group having a carbon number of 1 to20, a hydrocarbon group containing an oxygen atom or a nitrogen atom andhaving a carbon number of 1 to 20, a hydrocarbon group-substituted aminogroup having a carbon number of 1 to 20, or an alkoxy group having acarbon number of 1 to 20; Q^(11b) represents a carbon atom, a siliconatom or a germanium atom; each R^(11b) independently represents ahydrogen atom or a hydrocarbon group having a carbon number of 1 to 10and two R^(11b) may combine with each other to form a ring together withQ^(11b); each of R^(12b) and R^(14b) independently represents a hydrogenatom, a halogen atom, a hydrocarbon group having a carbon number of 1 to20, a silicon-containing hydrocarbon group containing from 1 to 6silicons and having a carbon number of 1 to 18, a halogen-containinghydrocarbon group having a carbon number of 1 to 20, a hydrocarbon groupcontaining an oxygen atom or a sulfur atom and having a carbon number of1 to 40, or a silyl group substituted with a hydrocarbon group having acarbon number of 1 to 40, provided that R^(12b) and R^(14b) do not forma ring together with the carbon atoms to which these members are bonded;each of R^(16b) and R^(17b) independently represents a saturated orunsaturated divalent hydrocarbon group having a carbon number of 4 or 5for forming a condensed ring with the 5-membered ring to which R^(16b)or R^(17b) is bonded; each of R^(18b) and R^(19b) is an atom or a groupbonded to a carbon atom of R^(16b) or R^(17b) and each independentlyrepresents a hydrogen atom, a halogen atom, a hydrocarbon group having acarbon number of 1 to 20, a silicon-containing hydrocarbon groupcontaining from 1 to 6 silicons and having a carbon number of 1 to 18, ahalogen-containing hydrocarbon group having a carbon number of 1 to 20,a hydrocarbon group containing an oxygen atom or a sulfur atom andhaving a carbon number of 1 to 40, or a silyl group substituted with ahydrocarbon group having a carbon number of 1 to 40; each of p^(b) andq^(b) independently represents an integer of 0 to 10 and when each ofp^(b) and q^(b) is 2 or more, at least two R^(18b) or at least twoR^(19b) may form a ring together with the carbon atoms to which thesemembers are bonded].

In formula (6b), detailed definitions of M^(2b), X^(11b), X^(12b),Q^(11b) and R^(11b) follow the definitions in the description of formula(2b) above.

In formula (6b), each of R^(12b) and R^(14b) specifically includes anelement or a group selected from, for example, a hydrogen atom, achlorine atom, a bromine atom, an iodine atom, a methyl group, an ethylgroup, an n-propyl group, an i-propyl group, an n-butyl group, ani-butyl group, a tert-butyl group, an n-pentyl group, a neopentyl group,a cyclopentyl group, an n-hexyl group, a cyclohexyl group, a phenylgroup, a benzyl group, a 2-methylphenyl group, a 3-methylphenyl group, a4-methylphenyl group, a 3,5-dimethylphenyl group, a 4-tert-butylphenylgroup, a 3,5-di-tert-butylphenyl group, a bis(trimethylsilyl)methylgroup, a bis(tert-butyldimethylsilyl)methyl group, a bromomethyl group,a chloromethyl group, a 2-chloroethyl group, a 2-bromoethyl group, a2-bromopropyl group, a 3-bromopropyl group, a 2-bromocyclopentyl group,a 2,3-dibromocyclopentyl group, a 2-bromo-3-iodocyclopentyl group, a2,3-dibromocyclohexyl group, a 2-chloro-3-iodocyclohexyl group, a2-chlorophenyl group, a 4-chlorophenyl group, a2,3,4,5,6-pentafluorophenyl group, a 4-trifluoromethylphenyl group, atrimethylsilyl group, a tri-tert-butylsilyl group, adi-tert-butylmethylsilyl group, a tert-butyldimethylsilyl group, atriphenylsilyl group, a diphenylmethylsilyl group, a phenyldimethylsilylgroup, a furyl group, a tetrahydrofuryl group, a 2-methylfuryl group,and a 2-(trimethyl)silylfuryl group; specifically, each is preferably anelement or a group selected from a hydrogen atom, a methyl group, anethyl group, an n-propyl group, an i-propyl group, an n-butyl group, ani-butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group,a cyclohexyl group, a phenyl group, a trimethylsilyl group, a furylgroup, a 2-methylfuryl group and a 2-(trimethyl)silyl group; andspecifically, each is more preferably an element or a group selectedfrom a hydrogen atom, a methyl group, an n-butyl group, a tert-butylgroup, a phenyl group, a trimethylsilyl group, a 2-methylfuryl group anda 2-(trimethyl)silylfuryl group. Also, at least one member out ofR^(12b) located on the 2-position of the cyclopentadienyl ring andR^(14b) located on the same 2-position is more preferably a groupselected from a methyl group, an ethyl group, an n-propyl group, ani-propyl group, an n-butyl group, an i-butyl group, a tert-butyl group,an n-pentyl group, an n-hexyl group, a cyclohexyl group, a phenyl group,a trimethylsilyl group, a furyl group, a 2-methylfuryl group and a2-(trimethyl)silylfuryl group, still more preferably a group selectedfrom a methyl group, an n-butyl group, a tert-butyl group, a phenylgroup, a trimethylsilyl group, a 2-methylfuryl group and a2-(trimethyl)silylfuryl group.

Specific examples of the condensed cyclopentadienyl structure formed byR^(16b) and a cyclopentadienyl moiety to which R^(16b) is bonded,include the partial structures (I) to (VI). Among these specificexamples, (I), (III) and (VI) are preferred. Also, R^(18b) may besubstituted on these partial structures (I) to (VI).

The substituent R^(18b) includes, in addition to a hydrogen atom, forexample, a chlorine atom, a bromine atom, an iodine atom, a methylgroup, an ethyl group, an n-propyl group, an i-propyl group, an n-butylgroup, an i-butyl group, a tert-butyl group, an n-pentyl group, aneopentyl group, a cyclopentyl group, an n-hexyl group, a cyclohexylgroup, a phenyl group, a benzyl group, a 2-methylphenyl group, a3-methylphenyl group, a 4-methylphenyl group, a 4-tert-butylphenylgroup, a 3,5-dimethylphenyl group, a 3,5-di-tert-butylphenyl group, anaphthyl group, an anthracenyl group, a bis(trimethylsilyl)methyl group,a bis(tert-butyldimethylsilyl)methyl group, a bromomethyl group, achloromethyl group, a 2-chloroethyl group, a 2-bromoethyl group, a2-bromopropyl group, a 3-bromopropyl group, a 2-bromocyclopentyl group,a 2,3-dibromocyclopentyl group, a 2-bromo-3-iodocyclopentyl group, a2,3-dibromocyclohexyl group, a 2-chloro-3-iodocyclohexyl group, a2-chlorophenyl group, a 4-chlorophenyl group, a2,3,4,5,6-pentafluorophenyl group, a 2,6-dichloro-4-trimethylsilylphenylgroup, a trimethylsilyl group, a tri-tert-butylsilyl group, adi-tert-butylmethylsilyl group, a tert-butyldimethylsilyl group, atriphenylsilyl group, a diphenylmethylsilyl group, a phenyldimethylsilylgroup, a furyl group, a tetrahydrofuryl group, a 2-methylfuryl group,and a 2-(trimethyl)silylfuryl group. R^(18b) may form a ring togetherwith the carbon atom to which R^(18b) is bonded.

In formula (6b), each of R^(17b) and R^(19b) is also independentlydefined, similarly to R^(16b) and R^(18b).

As the olefin polymerization catalyst component according to the presentinvention, the metallocene compound of the component (A-2b) is alsopreferably a compound represented by the following formula (7b):

[in formula (7b). M^(2b) represents any one transition metal of Ti, Zrand Hf; each of X^(11b) and X^(12b) independently represents a hydrogenatom, a halogen atom, a hydrocarbon group having a carbon number of 1 to20, a hydrocarbon group containing an oxygen atom or a nitrogen atom andhaving a carbon number of 1 to 20, a hydrocarbon group-substituted aminogroup having a carbon number of 1 to 20, or an alkoxy group having acarbon number of 1 to 20; Q^(11b) represents a carbon atom, a siliconatom or a germanium atom; each R^(11b) independently represents ahydrogen atom or a hydrocarbon group having a carbon number of 1 to 10and two R^(11b) may combine with each other to form a ring together withQ^(11b); each of R^(12b), R^(14b) and R^(15b) independently representsan atom or a group selected from a hydrogen atom, a halogen atom, ahydrocarbon group having a carbon number of 1 to 20, asilicon-containing hydrocarbon group containing from 1 to 6 silicons andhaving a carbon number of 1 to 18, a halogen-containing hydrocarbongroup having a carbon number of 1 to 20, a hydrocarbon group containingan oxygen atom or a sulfur atom and having a carbon number of 1 to 40,and a silyl group substituted with a hydrocarbon group having a carbonnumber of 1 to 40, provided that at least one of R^(12b), R^(14b) andR^(15b) located on the 2-position and 5-position of bothcyclopentadienyl rings is not a hydrogen atom and R^(12b), R^(14b) andR^(15b) do not form a ring together with the carbon atoms to which thesemembers are bonded: R^(16b) represents a saturated or unsaturateddivalent hydrocarbon group having a carbon number of 4 or 5 for forminga condensed ring with the 5-membered ring to which R^(16b) is bonded;R^(18b) is an atom or a group bonded to a carbon atom of R^(16b) andeach independently represents a hydrogen atom, a halogen atom, ahydrocarbon group having a carbon number of 1 to 20, asilicon-containing hydrocarbon group containing from 1 to 6 silicons andhaving a carbon number of 1 to 18, a halogen-containing hydrocarbongroup having a carbon number of 1 to 20, a hydrocarbon group containingan oxygen atom or a sulfur atom and having a carbon number of 1 to 40,or a silyl group substituted with a hydrocarbon group having a carbonnumber of 1 to 40; p^(b) represents an integer of 0 to 10 and when p^(b)is 2 or more, at least two R^(18b) may form a ring together with thecarbon atoms to which these members are bonded].

In formula (7b), detailed definitions of M^(2b), X^(11b), X^(12b),Q^(11b), R^(11b), R^(16b) and R^(18b) follow the definitions in thedescription of formula (6b) above.

In formula (7b), each of R^(12b), R^(14b) and R^(15b) specificallyincludes an element or a group selected from, for example, a hydrogenatom, a chlorine atom, a bromine atom, an iodine atom, a methyl group,an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group,an i-butyl group, a tert-butyl group, an n-pentyl group, a neopentylgroup, a cyclopentyl group, an n-hexyl group, a cyclohexyl group, aphenyl group, a benzyl group, a 2-methylphenyl group, a 3-methylphenylgroup, a 4-methylphenyl group, a 3,5-dimethylphenyl group, a4-tert-butylphenyl group, a 3,5-di-tert-butylphenyl group, abis(trimethylsilyl)methyl group, a bis(tert-butyldimethylsilyl)methylgroup, a bromomethyl group, a chloromethyl group, a 2-chloroethyl group,a 2-bromoethyl group, a 2-bromopropyl group, a 3-bromopropyl group, a2-bromocyclopentyl group, a 2,3-dibromocyclopentyl group, a2-bromo-3-iodocyclopentyl group, a 2,3-dibromocyclohexyl group, a2-chloro-3-iodocyclohexyl group, a 2-chlorophenyl group, a4-chlorophenyl group, a 2,3,4,5,6-pentafluorophenyl group, a4-trifluoromethylphenyl group, a trimethylsilyl group, atri-tert-butylsilyl group, a di-tert-butylmethylsilyl group, atert-butyldimethylsilyl group, a triphenylsilyl group, adiphenylmethylsilyl group, a phenyldimethylsilyl group, a furyl group, atetrahydrofuryl group, a 2-methylfuryl group, and a2-(trimethyl)silylfuryl group, provided that at least one of R^(12b),R^(14b) and R^(15b) located on the 2-position and 5-position of bothcyclopentadienyl rings is not a hydrogen atom; specifically, each ispreferably an element or a group selected from a hydrogen atom, a methylgroup, an ethyl group, an n-propyl group, an i-propyl group, an n-butylgroup, an i-butyl group, a tert-butyl group, an n-pentyl group, ann-hexyl group, a cyclohexyl group, a phenyl group, a trimethylsilylgroup, a furyl group, a 2-methylfuryl group and a 2-(trimethyl)silylgroup, provided that at least one of R^(12b). R^(14b) and R^(15b)located on the 2-position and 5-position of both cyclopentadienyl ringsis not a hydrogen atom; and specifically, each is more preferably anelement or a group selected from a hydrogen atom, a methyl group, ann-butyl group, a tert-butyl group, a phenyl group, a trimethylsilylgroup, a 2-methylfuryl group and a 2-(trimethyl)silylfuryl group,provided that at least one of R^(12b), R^(14b) and R^(15b) located onthe 2-position and 5-position of both cyclopentadienyl rings is not ahydrogen atom. In formula (7b), R^(12b) located on the 2-position of thecyclopentadienyl ring is more preferably an atom or a group selectedfrom a hydrocarbon group having a carbon number of 1 to 20, asilicon-containing hydrocarbon group containing from 1 to 6 silicons andhaving a carbon number of 1 to 18, a halogen-containing hydrocarbongroup having a carbon number of 1 to 20, a hydrocarbon group containingan oxygen atom or a sulfur atom and having a carbon number of 1 to 40,and a silyl group substituted with a hydrocarbon group having a carbonnumber of 1 to 40; still more preferably a group selected from a methylgroup, an ethyl group, an n-propyl group, an i-propyl group, an n-butylgroup, an i-butyl group, a tert-butyl group, an n-pentyl group, ann-hexyl group, a cyclohexyl group, a phenyl group, a trimethylsilylgroup, a furyl group, a 2-methylfuryl group and a2-(trimethyl)silylfuryl group: and most preferably a group selected froma methyl group, an n-butyl group, a tert-butyl group, a phenyl group, atrimethylsilyl group, a 2-methylfuryl group and a2-(trimethyl)silylfuryl group. In formula (7b). R^(12b), R^(14b) andR^(15b) do not form a ring together with the carbon atoms to which thesemembers are bonded.

As the olefin polymerization catalyst component according to the presentinvention, the metallocene compound of the component (A-2b) is morepreferably a compound represented by the following formula (8b):

[in formula (8b), M^(2b) represents any one transition metal of Ti, Zrand Hf; each of X^(11b) and X^(12b) independently represents a hydrogenatom, a halogen atom, a hydrocarbon group having a carbon number of 1 to20, a hydrocarbon group containing an oxygen atom or a nitrogen atom andhaving a carbon number of 1 to 20, a hydrocarbon group-substituted aminogroup having a carbon number of 1 to 20, or an alkoxy group having acarbon number of 1 to 20; Q^(11b) represents a carbon atom, a siliconatom or a germanium atom; each R^(11b) independently represents ahydrogen atom or a hydrocarbon group having a carbon number of 1 to 10and two R^(12b) may combine with each other to form a ring together withQ^(11b); each of R^(12b), R^(14b), R^(18b) and R^(19b) independentlyrepresents a hydrogen atom, a halogen atom, a hydrocarbon group having acarbon number of 1 to 20, a silicon-containing hydrocarbon groupcontaining from 1 to 6 silicons and having a carbon number of 1 to 18, ahalogen-containing hydrocarbon group having a carbon number of 1 to 20,a hydrocarbon group containing an oxygen atom or a sulfur atom andhaving a carbon number of 1 to 40, or a silyl group substituted with ahydrocarbon group having a carbon number of 1 to 40, provided thatR^(12b) and R^(14b) do not form a ring together with the carbon atoms towhich these members are bonded; and R^(18b) and R^(19b) may form a ringtogether with the carbon atoms to which these members are bonded].

In formula (8b), detailed definitions of M^(2b), X^(11b), X^(12b),Q^(11b), R^(11b), R^(12b), R^(14b), R^(18b) and R^(19b) follow thedefinitions in the description of formula (6b) above.

As the olefin polymerization catalyst component according to the presentinvention, the metallocene compound of the component (A-2b) is also morepreferably a compound represented by the following formula (9b):

[in formula (9b), M^(2b) represents any one transition metal of Ti, Zrand Hf; each of X^(11b) and X^(12b) independently represents a hydrogenatom, a halogen atom, a hydrocarbon group having a carbon number of 1 to20, a hydrocarbon group containing an oxygen atom or a nitrogen atom andhaving a carbon number of 1 to 20, a hydrocarbon group-substituted aminogroup having a carbon number of 1 to 20, or an alkoxy group having acarbon number of 1 to 20; Q^(11b) represents a carbon atom, a siliconatom or a germanium atom; each R^(11b) independently represents ahydrogen atom or a hydrocarbon group having a carbon number of 1 to 10and two R^(11b) may combine with each other to form a ring together withQ^(11b); each of R^(12b), R^(14b) and R^(15b) independently represents ahydrogen atom, a halogen atom, a hydrocarbon group having a carbonnumber of 1 to 20, a silicon-containing hydrocarbon group containingfrom 1 to 6 silicons and having a carbon number of 1 to 18, ahalogen-containing hydrocarbon group having a carbon number of 1 to 20,a hydrocarbon group containing an oxygen atom or a sulfur atom andhaving a carbon number of 1 to 40, or a silyl group substituted with ahydrocarbon group having a carbon number of 1 to 40, provided that atleast one of R^(12b) located on the 2-position of the indenyl ring andR^(14b) and R^(15b) located on the 2-position and 5-position of thecyclopentadienyl ring is not a hydrogen atom and R^(12b), R^(14b) andR^(15b) do not form a ring together with the carbon atoms to which thesemembers are bonded; and R^(18b) may form a ring together with the carbonatom to which R^(11b) is bonded].

In formula (9b), detailed definitions of M^(2b), X^(11b), X^(12b),Q^(11b), R^(11b), R^(12b), R^(14b), R^(15b) and R^(18b) follow thedefinitions in the description of formula (6b) above.

As the olefin polymerization catalyst component according to the presentinvention, the metallocene compound of the component (A-2b) is, out ofthe compounds represented by formulae (2b) and (6b) to (9b), preferablya compound where R^(12b) as a substituent on the 2-position of theconjugated 5-membered ring is a halogen atom, an alkyl group having acarbon number of 1 to 6, an alkoxy group having a carbon number of 1 to6, a phenoxy group having a carbon number of 6 to 12, an alkenyl grouphaving a carbon number of 2 to 8, a halogen-containing alkyl grouphaving a carbon number of 1 to 6, an aryl group having a carbon numberof 6 to 18, a halogen-containing aryl group having a carbon number of 6to 18, an alkyl group having a carbon number of 1 to 3 and containing atrialkylsilyl group with the alkyl group having a carbon number of 1 to3, a silyl group containing a hydrocarbon group having a carbon numberof 1 to 6, an oxygen-containing heterocyclic group or asulfur-containing heterocyclic group. Such a preferred substituentR^(12b) on the 2-position specifically includes, for example, a chlorineatom, a bromine atom, an iodine atom, a methyl group, an ethyl group, ann-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, atert-butyl group, an n-pentyl group, a neopentyl group, a cyclopentylgroup, an n-hexyl group, a cyclohexyl group, a phenyl group, a benzylgroup, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenylgroup, a 3,5-dimethylphenyl group, a 4-tert-butylphenyl group, a3,5-di-tert-butylphenyl group, a bis(trimethylsilyl)methyl group, abis(tert-butyldimethylsilyl)methyl group, a bromomethyl group, achloromethyl group, a 2-chloroethyl group, a 2-bromoethyl group, a2-bromopropyl group, a 3-bromopropyl group, a 2-bromocyclopentyl group,a 2,3-dibromocyclopentyl group, a 2-bromo-3-iodocyclopentyl group, a2,3-dibromocyclohexyl group, a 2-chloro-3-iodocyclohexyl group, a2-chlorophenyl group, a 4-chlorophenyl group, a2,3,4,5,6-pentafluorophenyl group, a 4-trifluoromethylphenyl group, atrimethylsilyl group, a tri-tert-butylsilyl group, adi-tert-butylmethylsilyl group, a tert-butyldimethylsilyl group, atriphenylsilyl group, a diphenylmethylsilyl group, and aphenyldimethylsilyl group; specifically, is more preferably a methylgroup, an ethyl group, an n-propyl group, an i-propyl group, an n-butylgroup, an i-butyl group, a tert-butyl group, an n-pentyl group, ann-hexyl group, a cyclohexyl group, a phenyl group or a trimethylsilylgroup: and specifically, is still more preferably a methyl group, ann-butyl group, a tert-butyl group, a phenyl group or a trimethylsilylgroup.

Other specific examples of the chemical structure for the preferredsubstituent R^(12b) on the 2-position include an oxygen-containingheterocyclic group and a sulfur-containing heterocyclic group,represented by the following formula (10b):

In formula (10b), R^(21b) and R^(22b) may be the same as or differentfrom each other and is a hydrogen atom, a halogen atom, an alkyl grouphaving a carbon number of 1 to 6, an alkoxy group having a carbon numberof 1 to 6, an alkenyl group having a carbon number of 2 to 8, ahalogen-containing alkyl group having a carbon number of 1 to 6, an arylgroup having a carbon number of 6 to 18, a halogen-containing aryl grouphaving a carbon number of 6 to 18, an alkyl group having a carbon numberof 1 to 3 and containing a trialkylsilyl group with the alkyl grouphaving a carbon number of 1 to 3, or a silyl group containing ahydrocarbon group having a carbon number of 1 to 6. Both of R^(21b) andR^(22b) may together constitute a 6- or 7-membered ring, and the 6- or7-membered ring may contain an unsaturated bond.

Here, specific examples of the alkyl group having a carbon number of 1to 6 include a methyl group, an ethyl group, an n-propyl group, ani-propyl group, an n-butyl group, an i-butyl group, a s-butyl group, atert-butyl group, an n-pentyl group, an n-hexyl group, a cyclopropylgroup, a cyclopentyl group, and a cyclohexyl group.

Specific examples of the alkoxy group having a carbon number of 1 to 6include a methoxy group, an ethoxy group, an n-propoxy group, ani-propoxy group, an n-butoxy group, an i-butoxy group, a tert-butoxygroup, and a phenoxy group. The halogen atom includes a chlorine atom, abromine atom, an iodine atom, and a fluorine atom. Specific examples ofthe alkenyl group having a carbon number of 2 to 8 include a vinylgroup, a propenyl group, an allyl group, a butenyl group, and acyclohexenyl group. Furthermore, the halogen atom in thehalogen-containing alkyl group having a carbon number of 1 to 6 includesa fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.The halogen-containing alkyl group having a carbon number of 1 to 6 is agroup where a hydrogen atom on the skeleton of an alkyl group having acarbon number of 1 to 6 is substituted for by a halogen atom, andspecific examples thereof include fluoromethyl, difluoromethyl,trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl,bromomethyl, dibromomethyl, tribromomethyl, iodomethyl,2,2,2-trifluoroethyl, 2,2,1,1-tetrafluoroethyl, pentafluoroethyl,pentachloroethyl, pentafluoropropyl, nonafluorobutyl, 5-chloropentyl,5,5,5-trichloropentyl, 5-fluoropentyl, 5,5,5-trifluoropentyl,6-chlorohexyl, 6,6,6-trichlorohexyl, 6-fluorohexyl, and6,6,6-trifluorohexyl. The aryl group having a carbon number of 6 to 18may be substituted with a hydrocarbon group having a carbon number of 1to 6, and specific examples include phenyl, tolyl, dimethylphenyl,ethylphenyl, trimethylphenyl, tert-butylphenyl, biphenyl, 1-naphthyl,2-naphthyl, acenaphthyl, phenanthryl, and anthryl. Specific examples ofthe halogen-containing aryl group having a carbon number of 6 to 18 arethose where a hydrogen atom of the above-described aryl group having acarbon number of 6 to 18 is substituted for by a halogen atom, andspecific examples include a 2-, 3- or 4-substituted fluorophenyl, a 2-,3- or 4-substituted chlorophenyl, a 2-, 3- or 4-substituted bromophenyl,a 2,4-, 2,5-, 2,6- or 3,5-substituted difluorophenyl, a 2,4-, 2,5-, 2,6-or 3,5-substituted dichlorophenyl, a 2,4,6-, 2,3,4-, 2,4,5- or3,4,5-substituted trifluorophenyl, a 2,4,6-, 2,3,4-, 2,4,5- or3,4,5-substituted trichlorophenyl, pentafluorophenyl, pentachlorophenyl,3,5-dimethyl-4-chlorophenyl, and 3,5-dichloro-4-biphenyl. The alkylgroup having a carbon number of 1 to 3 and containing a trialkylsilylgroup with the alkyl group having a carbon number of 1 to 3 is a groupwhere a hydrogen atom of an alkyl group having a carbon number of 1 to 3is substituted for by a trialkylsilyl group containing an alkyl grouphaving a carbon number of 1 to 3, which may be different, and specificexamples thereof include a trimethylsilylmethyl and atrimethylsilylethyl. The silyl group containing a hydrocarbon grouphaving a carbon number of 1 to 6 is a substituent where threehydrocarbon group having a carbon number of 1 to 6, which may bedifferent, are substituted on silicon. The hydrocarbon having a carbonnumber of 1 to 6 includes an alkyl group having a carbon number of 1 to6, alkoxy group having a carbon number of 1 to 6, an alkenyl grouphaving a carbon number of 2 to 8, a halogen-containing alkyl grouphaving a carbon number of 1 to 6, and a phenyl group, which aredescribed above, and a substituent may be substituted on the phenylgroup. The silyl group containing a hydrocarbon group specificallyincludes trimethylsilyl, triethylsilyl, tri-n-butylsilyl,tert-butyldimethylsilyl, trivinylsilyl, triallylsilyl, andtriphenylsilyl.

Each of R^(21b) and R^(22b) is independently, preferably hydrogen atom,a halogen atom, an alkyl group having a carbon number of 1 to 6, an arylgroup having a carbon number of 6 to 18, or a silyl group containing ahydrocarbon group having a carbon number of 1 to 6. In the case whereR^(21b) is a hydrogen atom, the synthesis yield is low, and R^(21b) ispreferably a substituent except for a hydrogen atom. R^(21b) is morepreferably an alkyl group having a carbon number of 1 to 6, an arylgroup having a carbon number of 6 to 18, or a silyl group containing ahydrocarbon group having a carbon number of 1 to 6. R^(22b) is morepreferably a hydrogen atom or an alkyl group having a carbon number of 1to 6. As for specific preferred substituents, R^(21b) is a methyl group,an ethyl group, a tert-butyl group, a cyclohexyl group, a phenyl group,a trimethylsilyl group or a triphenylsilyl group, and R^(22b) is ahydrogen atom, a methyl group or an ethyl group.

Both of R^(21b) and R^(22b) may together constitute a 6- or 7-memberedring, and the 6- or 7-membered ring may contain an unsaturated bond. Asfor specific substitution, the substituent on the 2-position of theindene ring includes a benzofuryl group and a benzothienyl group.

In the olefin polymerization catalyst component of the presentinvention, specific examples of the metallocene compound as thecomponent (A-2b) of the olefin polymerization catalyst component arerecited below, but the present invention is not limited thereto.

(i) Examples include: metallocene compounds classified into the bridgedCp₂Zr type; out of compounds recited in the above-described literaturessuch as JP-A-2-76887, JP-A-3-12406, JP-A-3-12407, JP-A-3-12407,JP-A-11-315089, JP-A-2009-143901 and JP-T-2005-507961, bridgedbis(alkyl-substituted cyclopentadienyl)zirconium compounds belonging toformula (2b); and out of zirconium compounds having a cyclopentadienylring substituted, for example, with an oxygen-containing hydrocarbongroup, a sulfur-containing hydrocarbon group or a hydrocarbongroup-substituted silyl group described in JP-T-2002-535339 and the likeand belonging to formula (2b), bridged bis(alkyl-substitutedcyclopentadienyl)zirconium compounds belonging to formula (2b).

Metallocene compounds classified into the bridged Cp₂Zr type are shownin Table b-9 and Table b-10.

TABLE 25 [Table b-9] (i) Bridged Cp2Zr Type

No. A1 A2 A3 A4 A5 142b Me2Si 2,3-Me2 2-Me Cl Cl A B C 143b Me2Si2,3-Me2 3-Me Cl Cl B 144b Me2Si 2,3-Me2 4-Me Cl Cl B 145b Me2Si 2,3-Me25-Me Cl Cl B C 146b Me2Si 2,3-Me2 2-Et Cl Cl B C 147b Me2Si 2,3-Me2 3-EtCl Cl B 148b Me2Si 2,3-Me2 2-iPr Cl Cl B C 149b Me2Si 2,3-Me2 3-iPr ClCl B 150b Me2Si 2,3-Me2 2-nBu Cl Cl B C 151b Me2Si 2,3-Me2 3-tBu Cl Cl B152b Me2Si 2,3-Me2 3-Ph Cl Cl B 153b Me2Si 2,4,5-Me3 — Cl Cl 154b Me2Si2-Et-4,5-Me2 — Cl Cl 155b Me2Si 2-Et-4-Bu-5-Me — Cl Cl 156b Me2Si2,4,5-Me3 2-Me Cl Cl B C 157b Me2Si 2-Et-4,5-Me2 3-tBu Cl Cl A B 158bMe2Si 2,3,4,5-Me4 — Cl Cl A 159b Me2Si 2,3,4,5,-Me4 2-Me Cl Cl A B C160b Me2Si 2,3-Me2 2,3-Me2 Cl Cl A B C 161b Me2Si 2,3,-Me2 2,3,-Me2 BrBr A B C 162b Me2Si 2,3-Me2 2,3-Me2 Me Me A B C 163b Me2Si 2,3,-Me22,3,-Me2 Ph Ph A B C 164b Me2Si 2,4,5-Me3 2,4,5-Me3 Cl Cl A B C 165bMe2Si 2-Et-4,5-Me2 2-Et-4,5- Cl Cl A B C Me2

TABLE b-10 (i) Bridged Cp2Zr Type (continued) No. A1 A2 A3 A4 A5 166bMe2Si 2-Et-4-Bu-5-Me 2-Et-4-Bu-5-Me Cl Cl A B C 167b Me2Si 2,3,4-Me32,3,4-Me3 Cl Cl A B C 168b Me2Si 2-Et-3,5-Me2 2-Et-3,5-Me2 Cl Cl A B C169b Me2Si 2,3,4,5-Me4 2,3,4,5-Me4 Cl Cl A B C 170b Me2Si 2,3,5-Me32,3,5-Me3 Cl Cl A B C 171b Me2Si TMS 2-Ind Cl Cl A B 172b Me2Si 1-Ind2-Ind Cl Cl A B 173b Me2Si 3-(2-furyl)-2,5-dimethyl3-(2-furyl)-2,5-dimethyl Cl Cl A B C 174b Me2Si 2-(2-furyl)-3,5-dimethyl2-(2-furyl)-3,5-dimethyl Cl Cl A B C 175b Me2Si 2-(2-furyl)-4,5-dimethyl2-(2-furyl)-4,5-dimethyl Cl Cl A B C 176b Me2Si3-(2-thienyl)-2,5-dimethyl 3-(2-thienyl)-2,5-dimethyl Cl Cl A B C 177bMe2Si 2-(2-thienyl)-4,5-dimethyl 2-(2-thienyl)-4,5-dimethyl Cl Cl A B C178b Me2Si 2-(5-methyl-2-furyl)-4,5- 2-(5-methyl-2-furyl)-4,5- Cl Cl A BC dimethyl dimethyl 179b Me2Si 2-(5-tert-butyl-2-furyl)-4,5-2-(5-tert-butyl-2-furyl)-4,5- Cl Cl A B C dimethyl dimethyl 180b Me2Si2-(5-trimethylsilyl-2-furyl)- 2-(5-trimethylsilyl-2-furyl)- Cl Cl A B C4,5-dimethyl 4,5-dimethyl 181b Me2Si 2-(4,5-dimethyl-2-furyl)-4,5-2-(4,5-dimethyl-2-furyl)-4,5- Cl Cl A B C dimethyl dimethyl 182b Me2Si2-(2-benzofuryl)-4,5-dimethyl 2-(2-benzofuryl)-4,5-dimethyl Cl Cl A B C183b Me2C 2-(2-furyl)-3-methyl 2-(2-furyl)-3-methyl Cl Cl A B C 184bMe2C 2-(2-furyl)-3,5-dimethyl 2-(2-furyl)-3,5-dimethyl Cl Cl B C 185bMe2C 2-(2-furyl)-4-ethyl-5-methyl 2-(2-furyl)-4-ethyl-5-methyl Cl Cl B C186b Me2C 2-(2-furyl)-4-isopropyl-5- 2-(2-furyl)-4-isopropyl-5- Cl Cl BC methyl methyl 187b Me2C 2-(2-furyl)-4-tert-butyl-5-2-(2-furyl)-4-tert-butyl-5- Cl Cl B C methyl methyl 188b Me2C2-(2-furyl)-4-phenyl-5-methyl 2-(2-furyl)-4-phenyl-5-methyl Cl Cl B C

(ii) Examples include metallocene compounds classified into the bridgedInd₂Zr type; out of compounds recited in the above-described literaturessuch as JP-A-8-59724, JP-A-10-231314, JP-A-2003-105029 andJP-A-2004-352707, bridged bis(substituted or unsubstitutedindenyl)zirconium compounds, bridged bis(substituted or unsubstitutedazulenyl)zirconium compounds and bridged (substituted or unsubstitutedindenyl)(substituted or unsubstituted azulenyl)zirconium compoundsbelonging to formula (6b) and formula (8b); and out of compounds recitedin the above-described literatures such as JP-T-2002-535339 andJP-A-2004-352707, zirconium compounds having an indenyl or azulenyl ringsubstituted, for example, with an oxygen-containing hydrocarbon group, asulfur-containing hydrocarbon group or a hydrocarbon group-substitutedsilyl group and belonging to formula (6b) and formula (8b).

Metallocene compounds classified into the bridged Ind₂Zr type are shownin Table b-11 and Table b-12.

TABLE 27 [Table b-11] (ii) Bridged Ind2Zr Type

No. A1 A2 A3 A4 189b Me2Si Ind Ind Cl A B 190b Me2Si Ind Ind Me A B 191bMe2Si Ind Ind Ph A B 192b Me2C Ind Ind Cl B 193b Me2Si H4Ind H4Ind Cl AB 194b PhMeSi H4Ind H4Ind Cl A B 195b Me2Si 2,4,4-Me3-H4Ind2,4,4-Me3-H4Azu Cl A B C 196b Me2Si 2-Me-Ind 2-Me-Ind Cl A B C 197bMe2Si 2,4-Me2-Ind 2,4-Me2-Ind Cl A B C 198b Me2Si 2-Me-4-Ph-Ind2-Me-4-Ph-Ind Cl A B C 199b Me2Si 2-Me-4,5-BenInd 2-Me-4,5-BenInd Cl A BC 200b Me2Si 2,4-Me2-H6Azu 2,4-Me2-H6Azu Cl A B C 201b Me2Si2,4-Me2-H4Ind 2,4-Me2-H4Ind Cl A B C 202b Me2C 2-Me-4-(4-BiPh)-Azu2-Me-4-(4-BiPh)-Azu Cl B C 203b Me2Si 2-Me-4-Ph-Ind 2,4-Ph2-Ind Cl A B C204b Me2Si 2-Me-4-Ph-Ind 2-iPr-4-Ph Cl A B C 205b Me2Si2-Me-4-(p-tBu-Ph)-Ind 2-iPr-4-(p-tBu-Ph)-Ind Cl A B C 206b Me2Si2-(2-furyl)-indenyl 2-(2-furyl)-indenyl Cl A B C 207b Me2Ge2-(2-furyl)-indenyl 2-(2-furyl)-indenyl Cl 208b Me2Si2-(2-thienyl)-indenyl 2-(2-thienyl)-indenyl Cl A B C 209b H2C(2-(2-furyl)-indenyl (2-(2-furyl)-indenyl Cl B C 210b Me2C2-(2-furyl)-indenyl 2-(2-furyl)-indenyl Cl B C 211b Me2Si2-(2-furyl)-4,5,6,7- 2-(2-furyl)-4,5,6,7- Cl A B C tetrahydroindenyltetrahydroindenyl 212b Me2C 2-(2-furyl)-7-methyl-indenyl2-(2-furyl)-7-methyl-indenyl Cl B C 213b Me2C2-(2-furyl)-4-methyl-indenyl 2-(2-furyl)-4-methyl-indenyl Cl B C 214hMe2C 2-(2-furyl)-3-methyl-indenyl 2-(2-furyl)-3-methyl-indenyl Cl B C215b Me2C 2-(2-furyl)-3,7-dimethyl- 2-(2-furyl)-3,7-dimethyl- Cl B Cindenyl indenyl 216b Me2C 2-(2-furyl)-4-chloro-indenyl2-(2-furyl)-4-chloro-indenyl Cl B C 217b Me2C2-(2-furyl)-4-phenyl-indenyl 2-(2-furyl)-4-phenyl-indenyl Cl A B C

TABLE b-12 (ii) Bridged Ind2Zr Type (continued) No. A1 A2 A3 A4 218bMe2C 2-(2-furyl)-4-methoxy-indenyl 2-(2-furyl)-4-methoxy-indenyl Cl B C219b Me2C 2-(2-furyl)-4-phenoxy-indenyl 2-(2-furyl)-4-phenoxy-indenyl ClB C 220b Me2C 2-(2-furyl)-4-trimethylsilyl-2-(2-furyl)-4-trimethylsilyl- Cl B C indenyl indenyl 221b Me2Si2-(2-furyl)-4-phenyl-indenyl 2-(2-furyl)-4-phenyl-indenyl Cl B C 222bMe2Si 2-(2-furyl)-4-phenyl-indenyl 2-(2-furyl)-4-phenyl-indenyl Me A B C223b Me2Si 2-(2-thienyl)-4-phenyl-indenyl 2-(2-thienyl)-4-phenyl-indenylCl A B C 224b Me2Si 2-(3-furyl)-4-phenyl-indenyl2-(3-furyl)-4-phenyl-indenyl Cl A B C 225b Me2Si2-(3-methyl-2-furyl)-indenyl 2-(3-methyl-2-furyl)-indenyl Cl A B C 226bMe2Si 2-(3-methyl-2-furyl))-4-phenyl- 2-(3-methyl-2-furyl))-4-phenyl- ClA B C indenyl indenyl 227b Me2Si 2-(2-furyl)-4-(4- 2-(2-furyl)-4-(4- ClA B C isopropylphenyl)-indenyl isopropylphenyl)-indenyl 228b Me2Si2-(2-furyl)-4,7-diphenyl- 2-(2-furyl)-4,7-diphenyl- Cl A B C indenylindenyl 229b Me2Si 2-(2-furyl)-4-phenyl-7-methyl-2-(2-furyl)-4-phenyl-7-methyl- Cl A B C indenyl indenyl 230b Me2Si2-(2-furyl)-4-chloro-indenyl 2-(2-furyl)-4-chloro-indenyl Cl A B C 231bMe2Si 2-(2-furyl)-4-phenyl-indenyl 2-(2-furyl)-4-phenyl-indenyl Cl A B C232b Me2Si 2-(2-furyl)-4-methoxy-indenyl 2-(2-furyl)-4-methoxy-indenylCl A B C 233b Me2Si 2,4-di(2-furyl)-indenyl 2,4-di(2-furyl)-indenyl Cl AB C 234b Me2Si 2-(2-furyl)-4-(2-thienyl)- 2-(2-furyl)-4-(2-thienyl)- ClA B C indenyl indenyl 235b Me2Si 2-(2-furyl)-4-(2-benzofuryl)-2-(2-furyl)-4-(2-benzofuryl)- Cl A B C indenyl indenyl 236b Me2Si2-(2-furyl)-benzoindenyl 2-(2-furyl)-benzoindenyl Cl A B C 237b Me2Si2-(2-furyl)-5,9-diethyl- 2-(2-furyl)-5,9-diethyl- Cl A B C benzindenylbenzindenyl 238b Me2Si 2-(2-furyl)-azulenyl 2-(2-furyl)-azulenyl Cl A BC 239b Me2Si 2-(4,5-dimethyl-2-furyl))- 2-(4,5-dimethyl-2-furyl))- Cl AB C azulenyl azulenyl 240b Me2Si 2-(5-trimethylsilyl-2-furyl))-2-(5-trimethylsilyl-2-furyl))- Cl A B C azulenyl azulenyl 241b Me2Si2-(2-furyl)-4-phenyl-azulenyl 2-(2-furyl)-4-phenyl-azulenyl Cl A B C242b Me2Si 2-methyl-4-phenyl-indenyl 2-(2-(5-methyl)-furyl)-4- Cl A B Cphenyl-indenyl 243b Me2Si 2-methyl-4-phenyl-indenyl2-(2-(5-methyl)-furyl)-4- Cl A B C phenyl-indenyl 244b Me2Si2-methyl-4-(1-naphthyl)indenyl 2-(2-(5-methylfuryl))-4-(1- Cl A B Cnaphthyl)indenyl 245b Me2Si 2-methyl-4-phenylindenyl2-(2-(5-methylthienyl))-4- Cl A B C phenylindenyl

(iii) Examples include metallocene compounds classified into the bridgedCpIndZr type; and out of compounds recited in the above-describedliteratures such as JP-A-6-87922, JP-A-8-92308, JP-A-9-873 14,JP-A-7-224079 and JP-A-2005-336092, zirconium compounds belonging toformula (7b) and formula (9b).

Metallocene compounds classified into the bridged CpIndZr type are shownin Table b-13 to Table b-20.

TABLE 29 [Table b-13] (iii) Bridged CpIndZr Type

No. A1 A2 A3 A4 246b Me2C 4-methyl-cyclopentadienyl 3-methyl-indenyl ClA B 247b Me2C 4-tert-butyl-cyclopentadienyl 3-methyl-indenyl Cl A B 248bMe2C 4-tert-butyl-cyclopentadienyl 3-tert-butyl-indenyl Cl A B 249bMe2Si 4-methyl-cyclopentadienyl 3-methyl-indenyl Cl A B 250b Me2Si4-tert-butyl-cyclopentadienyl 3-methyl-indenyl Cl A B 251b Me2Si4-tert-butyl-cyclopentadienyl 3-tert-butyl-indenyl Cl A B 252b Me2C4-methyl-cyclopentadienyl 3-methyl-indenyl Me A B 253b Me2C4-tert-butyl-cyclopentadienyl 3-methyl-indenyl Me A B 254b Me2C4-tert-butyl-cyclopentadienyl 3-tert-butyl-indenyl Me A B 255b Me2C3-tert-butylcyclopentadienyl 2-methylindenyl Cl A B C D 256b Me2Si2-methyl-4-phenyl-1-indenyl 2,3,5-trimethyl-1- Cl A B C Dcyclopentadienyl 257b Me2Si 2-methyl-benz[e]indenyl cyclopentadienyl ClA B C D 258b Me2C 2-methylindenyl cyclopentadienyl Cl B C D 259b Me2Si2-methyl-benz[e]indenyl 2-methylcyclopentadienyl Cl A B C D 260b Me2Si2,3,4,5-tetramethyl- 2-methyl-4-phenyl-4H-1- Cl A B C D cyclopentadienylazulenyl 261b Me2Si 2,3,4,5-tetramethyl- 2-methyl-4-phenyl-5,6,7,8- Cl AB C D cyclopentadienyl tetrahydro-4H-1-azulenyl 262b Me2Si2,3,4,5-tetramethyl- 2,4-dimethyl-4H-1-azulenyl Cl A B C Dcyclopentadienyl 263b Me2Si 2,3,4,5-tetramethyl- 2,4-dimethyl-5,6,7,8-Cl A B C D cyclopentadienyl tetrahydro-4H-1-azulenyl 264b Me2Si2,3,4,5-tetramethyl- 2-ethyl-4-phenyl-4H-1-azulenyl Cl A B C Dcyclopentadienyl 265b Me2Si 2,3,4,5-tetramethyl-2-ethyl-4-methyl-4H-1-azulenyl Cl A B C D cyclopentadienyl 266b Me2Sicyclopentadienyl 2-(5-methyl-2-furyl)indenyl Cl B C D E 267b Me2Si3-methylcyclopentadienyl 2-(5-methyl-2-furyl)indenyl Cl A B C D E 268bMe2Si 3-ethylcyclopentadienyl 2-(5-methyl-2-furyl)indenyl Cl A B C D E269b Me2Si 3-phenylcyclopentadienyl 2-(5-methyl-2-furyl)indenyl Cl A B CD E 270b Me2Si 3-tert-butylcyclopentadienyl 2-(5-methyl-2-furyl)indenylCl A B C D E 271b Me2Si 3-(trimethylsilyl)- 2-(5-methy1-2-furyl)indenylCl A B C D E cyclopentadienyl 272b Me2Si 2,4-dimethylcyclopentadienyl2-(5-methyl-2-furyl)indenyl Cl A B C D E

TABLE b-14 (iii) Bridged CpIndZr Type (continued) No. A1 A2 A3 A4 273bMe2Si 2-methyl-4-phenyl- 2-(5-methyl-2-furyl)indenyl Cl A B C D Ecyclopentadienyl) 274b Me2Si 2-methyl-4-(2-naphthyl)-2-(5-methyl-2-furyl)indenyl Cl A B C D E cyclopentadienyl 275b Me2Si2-methyl-4-tert-butyl- 2-(5-methyl-2-furyl)indenyl Cl A B C D Ecyclopentadienyl 276b Me2Si 2-methyl-4-trimethyl-2-(5-methyl-2-furyl)indenyl Cl A B C D E silylcyclopentadienyl 277bMe2Si 2-ethyl-4-i-propyl- 2-(5-methyl-2-furyl)indenyl Cl A B C D Ecyclopentadienyl 278b Me2Si 2,3,5-trimethyl- 2-(5-methyl-2-furyl)indenylCl A B C D E cyclopentadienyl 279b Me2Si 2,5-dimethyl-3-tert-butyl-2-(5-methyl-2-furyl)indenyl Cl A B C D E cyclopentadienyl 280b Me2Si2,3,4,5-tetramethyl- 2-(5-methyl-2-furyl)indenyl Cl A B C D Ecyclopentadienyl 281b Me2Si cyclopentadienyl 2-(5-methyl-2-furyl)-4- ClA B C D E phenylindenyl 282b Me2Si 3-methylcyclopentadienyl2-(5-methyl-2-furyl)-4- Cl A B C D E phenylindenyl 283b Me2Si3-ethylcyclopentadienyl 2-(5-methyl-2-furyl)-4- Cl A B C D Ephenylindenyl 284b Me2Si 3-phenylcyclopentadienyl2-(5-methyl-2-furyl)-4- Cl A B C D E phenylindenyl 285b Me2Si3-tert-butylcyclopentadienyl 2-(5-methyl-2-furyl)-4- Cl A B C D Ephenylindenyl 286b Me2Si 3-(trimethylsilyl)- 2-(5-methyl-2-furyl)-4- ClA B C D E cyclopentadienyl phenylindenyl 287b Me2Si2,4-dimethylcyclopentadienyl 2-(5-methyl-2-furyl)-4- Cl A B C D Ephenylindenyl 288b Me2Si 2-methyl-4-phenyl- 2-(5-methyl-2-furyl)-4- Cl AB C D E cyclopentadienyl phenylindenyl 289b Me2Si2-methyl-4-(2-naphthyl)- 2-(5-methyl-2-furyl)-4- Cl A B C D Ecyclopentadienyl phenylindenyl 290b Me2Si 2-methyl-4-tert-butyl-2-(5-methyl-2-furyl)-4- Cl A B C D E cyclopentadienyl phenylindenyl 291bMe2Si 2-methyl-4-trimethylsilyl- 2-(5-methyl-2-furyl)-4- Cl A B C D Ecyclopentadienyl phenylindenyl 292b Me2Si 2-ethyl-4-i-propyl-2-(5-methyl-2-furyl)-4- Cl A B C D E cyclopentadienyl phenylindenyl 293bMe2Si 2,3,5-trimethyl- 2-(5-methyl-2-furyl)-4- Cl A B C D Ecyclopentadienyl phenylindenyl 294b Me2Si 2,5-dimethyl-3-tert-butyl-2-(5-methyl-2-furyl)-4- Cl A B C D E cyclopentadienyl phenylindenyl 295bMe2Si 2,3,4,5-tetramethyl- 2-(5-methyl-2-furyl)-4- Cl A B C D Ecyclopentadienyl phenylindenyl

TABLE b-15 (iii) Bridged CpIndZr Type (continued) No. A1 A2 A3 A4 296bMe2Si cyclopentadienyl 2-(4,5-dimethyl-2-furyl)-4- Cl A B C D Ephenylindenyl 297b Me2Si 3-methylcyclopentadienyl2-(4,5-dimethyl-2-furyl)-4- Cl A B C D E phenylindenyl 298b Me2Si3-phenylcyclopentadienyl 2-(4,5-dimethyl-2-furyl)-4- Cl A B C D Ephenylindenyl 299b Me2Si 3-tert-butylcyclopentadienyl2-(4,5-dimethyl-2-furyl)-4- Cl A B C D E phenylindenyl 300b Me2Si3-(trimethylsilyl)- 2-(4,5-dimethyl-2-furyl)-4- Cl A B C D Ecyclopentadienyl phenylindenyl 301b Me2Si 2,4-dimethylcyclopentadienyl2-(4,5-dimethyl-2-furyl)-4- Cl A B C D E phenylindenyl 302b Me2Si2-methyl-4-phenyl- 2-(4,5-dimethyl-2-furyl)-4- Cl A B C D Ecyclopentadienyl phenylindenyl 303b Me2Si 2-methyl-4-tert-butyl-2-(4,5-dimethyl-2-furyl)-4- Cl A B C D E cyclopentadienyl phenylindenyl304b Me2Si 2,3,5-trimethyl- 2-(4,5-dimethyl-2-furyl)-4- Cl A B C D Ecyclopentadienyl phenylindenyl 305b Me2Si 2,3,4,5-tetramethyl-2-(4,5-dimethyl-2-furyl)-4- Cl A B C D E cyclopentadienyl phenylindenyl306b Me2Si cyclopentadienyl 2-(5-tert-butyl-2-furyl)-4- Cl A B C D Ephenylindenyl 307b Me2Si 3-methylcyclopentadienyl2-(5-tert-butyl-2-furyl)-4- Cl A B C D E phenylindenyl 308b Me2Si3-phenylcyclopentadienyl 2-(5-tert-butyl-2-furyl)-4- Cl A B C D Ephenylindenyl 309b Me2Si 3-tert-butylcyclopentadienyl2-(5-tert-butyl-2-furyl)-4- Cl A B C D E phenylindenyl 310b Me2Si3-(trimethylsilyl)- 2-(5-tert-butyl-2-furyl)-4- Cl A B C D Ecyclopentadienyl phenylindenyl 311b Me2Si 2,4-dimethylcyclopentadienyl2-(5-tert-butyl-2-furyl)-4- Cl A B C D E phenylindenyl 312b Me2Si2-methyl-4-phenyl- 2-(5-tert-butyl-2-furyl)-4- Cl A B C D Ecyclopentadienyl phenylindenyl 313b Me2Si 2-methyl-4-tert-butyl-2-(5-tert-butyl-2-furyl)-4- Cl A B C D E cyclopentadienyl phenylindenyl314b Me2Si 2,3,5-trimethyl- 2-(5-tert-butyl-2-furyl)-4- Cl A B C D Ecyclopentadienyl phenylindenyl 315b Me2Si 2,3,4,5-tetramethyl-2-(5-tert-butyl-2-furyl)-4- Cl A B C D E cyclopentadienyl phenylindenyl

TABLE b-16 (iii) Bridged CpIndZr Type (continued) No. A1 A2 A3 A4 316bMe2Si cyclopentadienyl 2-(5-phenyl-2-furyl)-4- Cl A B C D Ephenylindenyl 317b Me2Si 3-methylcyclopentadienyl2-(5-phenyl-2-furyl)-4- Cl A B C D E phenylindenyl 318b Me2Si3-phenylcyclopentadienyl 2-(5-phenyl-2-furyl)-4- Cl A B C D Ephenylindenyl 319b Me2Si 3-tert-butylcyclopentadienyl2-(5-phenyl-2-furyl)-4- Cl A B C D E phenylindenyl 320b Me2Si3-(trimethylsilyl)- 2-(5-phenyl-2-furyl)-4- Cl A B C D Ecyclopentadienyl phenylindenyl 321b Me2Si 2,4-dimethylcyclopentadienyl2-(5-phenyl-2-furyl)-4- Cl A B C D E phenylindenyl 322b Me2Si2-methyl-4-phenyl- 2-(5-phenyl-2-furyl)-4- Cl A B C D E cyclopentadienylphenylindenyl 323b Me2Si 2-methyl-4-tert-butyl- 2-(5-phenyl-2-furyl)-4-Cl A B C D E cyclopentadienyl phenylindenyl 324b Me2Si 2,3,5-trimethyl-2-(5-phenyl-2-furyl)-4- Cl A B C D E cyclopentadienyl phenylindenyl 325bMe2Si 2,3,4,5-tetramethyl- 2-(5-phenyl-2-furyl)-4- Cl A B C D Ecyclopentadienyl phenylindenyl 326b Me2Si cyclopentadienyl2-(4,5-benzo-2-furyl)-4- Cl A B C D E phenylindenyl 327b Me2Si3-methylcyclopentadienyl 2-(4,5-benzo-2-furyl)-4- Cl A B C D Ephenylindenyl 328b Me2Si 3-phenylcyclopentadienyl2-(4,5-benzo-2-furyl)-4- Cl A B C D E phenylindenyl 329b Me2Si3-tert-butylcyclopentadienyl 2-(4,5-benzo-2-furyl)-4- Cl A B C D Ephenylindenyl 330b Me2Si 3-(trimethylsilyl)- 2-(4,5-benzo-2-furyl)-4- ClA B C D E cyclopentadienyl phenylindenyl 331b Me2Si2,4-dimethylcyclopentadienyl 2-(4,5-benzo-2-furyl)-4- Cl A B C D Ephenylindenyl 332b Me2Si 2-methyl-4-phenyl- 2-(4,5-benzo-2-furyl)-4- ClA B C D E cyclopentadienyl phenylindenyl 333b Me2Si2-methyl-4-tert-butyl- 2-(4,5-benzo-2-furyl)-4- Cl A B C D Ecyclopentadienyl phenylindenyl 334b Me2Si 2,3,5-trimethyl-2-(4,5-benzo-2-furyl)-4- Cl A B C D E cyclopentadienyl phenylindenyl335b Me2Si 2,3,4,5-tetramethyl- 2-(4,5-benzo-2-furyl)-4- Cl A B C D Ecyclopentadienyl phenylindenyl

TABLE b-17 (iii) Bridged CpIndZr Type (continued) No. A1 A2 A3 A4 336bMe2Si cyclopentadienyl 2-(5-methyl-2-furyl)-4-(4- Cl A B C D Etert-butylphenyl)indenyl 337b Me2Si 3-methylcyclopentadienyl2-(5-methyl-2-furyl)-4-(4- Cl A B C D E tert-butylphenyl)indenyl 338bMe2Si 3-phenylcyclopentadienyl 2-(5-methyl-2-furyl)-4-(4- Cl A B C D Etert-butylphenyl)indenyl 339b Me2Si 3-tert-butylcyclopentadienyl2-(5-methyl-2-furyl)-4-(4- Cl A B C D E tert-butylphenyl)indenyl 340bMe2Si 3-(trimethylsilyl)- 2-(5-methyl-2-furyl)-4-(4- Cl A B C D Ecyclopentadienyl tert-butylphenyl)indenyl 341b Me2Si2,4-dimethylcyclopentadienyl 2-(5-methyl-2-furyl)-4-(4- Cl A B C D Etert-butylphenyl)indenyl 342b Me2Si 2-methyl-4-phenyl-2-(5-methyl-2-furyl)-4-(4- Cl A B C D E cyclopentadienyltert-butylphenyl)indenyl 343b Me2Si 2-methyl-4-tert-butyl-2-(5-methyl-2-furyl)-4-(4- Cl A B C D E cyclopentadienyltert-butylphenyl)indenyl 344b Me2Si 2,3,5-trimethyl-2-(5-methyl-2-furyl)-4-(4- Cl A B C D E cyclopentadienyltert-butylphenyl)indenyl 345b Me2Si 2,3,4,5-tetramethyl-2-(5-methyl-2-furyl)-4-(4- Cl A B C D E cyclopentadienyltert-butylphenyl)indenyl 346b Me2Si cyclopentadienyl2-(5-methyl-2-furyl)-4-(4-i- Cl A B C D E propylphenyl)indenyl 347bMe2Si 3-methylcyclopentadienyl 2-(5-methyl-2-furyl)-4-(4-i- Cl A B C D Epropylphenyl)indenyl 348b Me2Si 3-phenylcyclopentadienyl2-(5-methyl-2-furyl)-4-(4-i- Cl A B C D E propylphenyl)indenyl 349bMe2Si 3-tert-butylcyclopentadienyl 2-(5-methyl-2-furyl)-4-(4-i- Cl A B CD E propylphenyl)indenyl 350b Me2Si 3-(trimethylsilyl)-2-(5-methyl-2-furyl)-4-(4-i- Cl A B C D E cyclopentadienylpropylphenyl)indenyl 351b Me2Si 2,4-dimethylcyclopentadienyl2-(5-methyl-2-furyl)-4-(4-i- Cl A B C D E propylphenyl)indenyl 352bMe2Si 2-methyl-4-phenyl- 2-(5-methyl-2-furyl)-4-(4-i- Cl A B C D Ecyclopentadienyl propylphenyl)indenyl 353b Me2Si 2-methyl-4-tert-butyl-2-(5-methyl-2-furyl)-4-(4-i- Cl A B C D E cyclopentadienylpropylphenyl)indenyl 354b Me2Si 2,3,5-trimethyl-2-(5-methyl-2-furyl)-4-(4-i- Cl A B C D E cyclopentadienylpropylphenyl)indenyl 355b Me2Si 2,3,4,5-tetramethyl-2-(5-methyl-2-furyl)-4-(4-i- Cl A B C D E cyclopentadienylpropylphenyl)indenyl

TABLE b-18 (iii) Bridged CpIndZr Type (continued) No. A1 A2 A3 A4 356bMe2Si cyclopentadienyl 2-(5-methyl-2-furyl)-4-(4- Cl A B C D Echlorophenyl)indenyl 357b Me2Si 3-methylcyclopentadienyl2-(5-methyl-2-furyl)-4-(4- Cl A B C D E chlorophenyl)indenyl 358b Me2Si3-phenylcyclopentadienyl 2-(5-methyl-2-furyl)-4-(4- Cl A B C D Echlorophenyl)indenyl 359b Me2Si 3-tert-butylcyclopentadienyl2-(5-methyl-2-furyl)-4-(4- Cl A B C D E chlorophenyl)indenyl 360b Me2Si3-(trimethylsilyl)- 2-(5-methyl-2-furyl)-4-(4- Cl A B C D Ecyclopentadienyl chlorophenyl)indenyl 361b Me2Si2,4-dimethylcyclopentadienyl 2-(5-methyl-2-furyl)-4-(4- Cl A B C D Echlorophenyl)indenyl 362b Me2Si 2-methyl-4-phenyl-2-(5-methyl-2-furyl)-4-(4- Cl A B C D E cyclopentadienylchlorophenyl)indenyl 363b Me2Si 2-methyl-4-tert-butyl-2-(5-methyl-2-furyl)-4-(4- Cl A B C D E cyclopentadienylchlorophenyl)indenyl 364b Me2Si 2,3,5-trimethyl-2-(5-methyl-2-furyl)-4-(4- Cl A B C D E cyclopentadienylchlorophenyl)indenyl 365b Me2Si 2,3,4,5-tetramethyl-2-(5-methyl-2-furyl)-4-(4- Cl A B C D E cyclopentadienylchlorophenyl)indenyl 366b Me2Si cyclopentadienyl2-(5-methyl-2-furyl)-4-(3,5- Cl A B C D E di-tert-butylphenyl)indenyl367b Me2Si 3-methylcyclopentadienyl 2-(5-methyl-2-furyl)-4-(3,5- Cl A BC D E di-tert-butylphenyl)indenyl 368b Me2Si 3-phenylcyclopentadienyl2-(5-methyl-2-furyl)-4-(3,5- Cl A B C D E di-tert-butylphenyl)indenyl369b Me2Si 3-tert-butylcyclopentadienyl 2-(5-methyl-2-furyl)-4-(3,5- ClA B C D E di-tert-butylphenyl)indenyl 370b Me2Si 3-(trimethylsilyl)-2-(5-methyl-2-furyl)-4-(3,5- Cl A B C D E cyclopentadienyldi-tert-butylphenyl)indenyl 371b Me2Si 2,4-dimethylcyclopentadienyl2-(5-methyl-2-furyl)-4-(3,5- Cl A B C D E di-tert-butylphenyl)indenyl372b Me2Si 2-methyl-4-phenyl- 2-(5-methyl-2-furyl)-4-3,5- Cl A B C D Ecyclopentadienyl di-tert-butylphenyl)indenyl 373b Me2Si2-methyl-4-tert-butyl- 2-(5-methyl-2-furyl)-4-(3,5- Cl A B C D Ecyclopentadienyl di-tert-butylphenyl)indenyl 374b Me2Si 2,3,5-trimethyl-2-(5-methyl-2-furyl)-4-(3,5- Cl A B C D E cyclopentadienyldi-tert-butylphenyl)indenyl 375b Me2Si 2,3,4,5-tetramethyl-2-(5-methyl-2-furyl)-4-(3,5- Cl A B C D E cyclopentadienyldi-tert-butylphenyl)indenyl

TABLE b-19 (iii) Bridged CpIndZr Type (continued) No. A1 A2 A3 A4 376bMe2Si cyclopentadienyl 2-(5-methyl-2-furyl)-4-(2- Cl A B C D Emethylphenyl)indenyl 377b Me2Si 3-methylcyclopentadienyl2-(5-methyl-2-furyl)-4-(2- Cl A B C D E methylphenyl)indenyl 378b Me2Si3-phenylcyclopentadienyl 2-(5-methyl-2-furyl)-4-(2- Cl A B C D Emethylphenyl)indenyl 379b Me2Si 3-tert-butylcyclopentadienyl2-(5-methyl-2-furyl)-4-(2- Cl A B C D E methylphenyl)indenyl 380b Me2Si3-(trimethylsilyl)- 2-(5-methyl-2-furyl)-4-(2- Cl A B C D Ecyclopentadienyl methylphenyl)indenyl 381b Me2Si2,4-dimethylcyclopentadienyl 2-(5-methyl-2-furyl)-4-(2- Cl A B C D Emethylphenyl)indenyl 382b Me2Si 2-methyl-4-phenyl-2-(5-methyl-2-furyl)-4-(2- Cl A B C D E cyclopentadienylmethylphenyl)indenyl 383b Me2Si 2-methyl-4-tert-butyl-2-(5-methyl-2-furyl)-4-(2- Cl A B C D E cyclopentadienylmethylphenyl)indenyl 384b Me2Si 2,3,5-trimethyl-2-(5-methyl-2-furyl)-4-(2- Cl A B C D E cyclopentadienylmethylphenyl)indenyl 385b Me2Si 2,3,4,5-tetramethyl-2-(5-methyl-2-furyl)-4-(2- Cl A B C D E cyclopentadienylmethylphenyl)indenyl 386b Me2Si cyclopentadienyl2-(5-methyl-2-furyl)-3-methyl- Cl A B C D E 4-phenylindenyl 387b Me2Si3-methylcyclopentadienyl 2-(5-methyl-2-furyl)-3-methyl- Cl A B C D E4-phenylindenyl 388b Me2Si 3-tert-butylcyclopentadienyl2-(5-methyl-2-furyl)-3-methyl- Cl A B C D E 4-phenylindenyl 389b Me2Si2,4-dimethylcyclopentadienyl 2-(5-methyl-2-furyl)-3-methyl- Cl A B C D E4-phenylindenyl 390b Me2Si 2-methyl-4-phenyl-2-(5-methyl-2-furyl)-3-methyl- Cl A B C D E cyclopentadienyl4-phenylindenyl 391b Me2Si 2-methyl-4-tert-butyl-2-(5-methyl-2-furyl)-3-methyl- Cl A B C D E cyclopentadienyl4-phenylindenyl 392b Me2Si 2,3,5-trimethyl-2-(5-methyl-2-furyl)-3-methyl- Cl A B C D E cyclopentadienyl4-phenylindenyl 393b Me2Si 2,3,4,5-tetramethyl-2-(5-methyl-2-furyl)-3-methyl- Cl A B C D E cyclopentadienyl4-phenylindenyl 394b Me2Si cyclopentadienyl 2-(5-methyl-2-furyl)-3-n- ClA B C D E butyl-4-phenylindenyl 395b Me2Si 3-methylcyclopentadienyl2-(5-methyl-2-furyl)-3-n- Cl A B C D E butyl-4-phenylindenyl

TABLE b-20 (iii) Bridged CpIndZr Type (continued) No. A1 A2 A3 A4 396bMe2Si 3-tert-butylcyclopentadienyl 2-(5-methyl-2-furyl)-3-n- Cl A B C DE butyl-4-phenylindenyl 397b Me2Si 2,4-dimethylcyclopentadienyl(2-(5-methyl-2-furyl)-3-n- Cl A B C D E butyl-4-phenylindenyl 398b Me2Si2-methyl-4-phenyl- 2-(5-methyl-2-furyl)-3-n- Cl A B C D Ecyclopentadienyl butyl-4-phenylindenyl 399b Me2Si 2-methyl-4-tert-butyl-2-(5-methyl-2-furyl)-3-n- Cl A B C D E cyclopentadienylbutyl-4-phenylindenyl 400b Me2Si 2,3,5-trimethyl-2-(5-methyl-2-furyl)-3-n- Cl A B C D E cyclopentadienylbutyl-4-phenylindenyl 401b Me2Si 2,3,4,5-tetramethyl-2-(5-methyl-2-furyl)-3-n- Cl A B C D E cyclopentadienylbutyl-4-phenylindenyl 402b Me2Si cyclopentadienyl2-(5-methyl-2-furyl)-3-s- Cl A B C D E butyl-4-phenylindenyl 403b Me2Si3-methylcyclopentadienyl 2-(5-methyl-2-furyl)-3-s- Cl A B C D Ebutyl-4-phenylindenyl 404b Me2Si 3-tert-butylcyclopentadienyl2-(5-methyl-2-furyl)-3-s- Cl A B C D E butyl-4-phenylindenyl 405b Me2Si2,4-dimethylcyclopentadienyl 2-(5-methyl-2-furyl)-3-s- Cl A B C D Ebutyl-4-phenylindenyl 406b Me2Si 2-methyl-4-phenyl-2-(5-methyl-2-furyl)-3-s- Cl A B C D E cyclopentadienylbutyl-4-phenylindenyl 407b Me2Si 2-methyl-4-tert-butyl-2-(5-methyl-2-furyl)-3-s- Cl A B C D E cyclopentadienylbutyl-4-phenylindenyl 408b Me2Si 2,3,5-trimethyl-2-(5-methyl-2-furyl)-3-s- Cl A B C D E cyclopentadienylbutyl-4-phenylindenyl 409b Me2Si 2,3,4,5-tetramethyl-2-(5-methyl-2-furyl)-3-s- Cl A B C D E cyclopentadienylbutyl-4-phenylindenyl

The metallocene compound also includes, for example, compounds wherezirconium in the compounds above is replaced by titanium or hafnium. Inthe case of using these metallocene compounds as the component (A-2b),two or more thereof may be also used.

In specific compounds exemplified above, preferred metallocene compoundsas the component (A-2b) in view of polymerization activity are denotedby “A”. Examples of the compound preferred in view of highpolymerization activity include:1-indenyl-2-indenyl-dimethylsilylzirconium dichloride; out of compoundsrecited in the above-described literatures such as JP-A-2-76887,JP-A-3-12406, JP-A-3-12407, JP-A-3-12407, JP-A-11-315089,JP-A-2009-143901 and JP-T-2005-507961, silicon-bridgedbis(alkyl-substituted cyclopentadienyl)zirconium compounds belong toformula (2b), where the total number of alkyl substituents on twocyclopentadienyl rings is 4 or more; out of zirconium compounds having acyclopentadienyl ring substituted, for example, with anoxygen-containing hydrocarbon group, a sulfur-containing hydrocarbongroup or a hydrocarbon group-substituted silyl group described inJP-T-2002-535339 and the like and belonging to formula (2b), compoundshaving a silicon-bridged bis(substituted cyclopentadienyl) structure,where the total number of substituents on two cyclopentadienyl rings,including the oxygen-containing hydrocarbon group or the like, is 4 ormore; out of compounds recited in the above-described literatures suchas JP-A-8-59724, JP-A-10-231314, JP-A-2003-105029 and JP-A-2004-352707,silicon-bridged bis(substituted or unsubstituted indenyl)zirconiumcompounds, silicon-bridged bis(substituted or unsubstitutedazulenyl)zirconium compounds and silicon-bridged (substituted orunsubstituted indenyl)(substituted or unsubstituted azulenyl)zirconiumcompounds belonging to formula (6b) and formula (8b); out of compoundsrecited in the above-described literatures such as JP-T-2002-535339 andJP-A-2004-352707, silicon-bridged bis(substituted or unsubstitutedindenyl)zirconium compounds, silicon-bridged bis(substituted orunsubstituted azulenyl)zirconium compounds and silicon-bridged(substituted or unsubstituted indenyl)(substituted or unsubstitutedazulenyl)zirconium compounds, each having an indenyl or azulenyl ringsubstituted, for example, with an oxygen-containing hydrocarbon group, asulfur-containing hydrocarbon group or a hydrocarbon group-substitutedsilyl group and belonging to formula (6b) and formula (8b); and out ofcompounds recited in the above-described literatures such asJP-A-6-87922, JP-A-8-92308, JP-A-9-87314, JP-A-7-224079 andJP-A-2005-336092, zirconium compounds belonging to formula (7b) andformula (9b), where the total number of substituents which may be theabove-described oxygen-containing hydrocarbon group or the like, oncyclopentadienyl rings connected by a bridging group and on acyclopentadienyl ring having a co-ring is 2 or more.

Similarly, in specific compounds exemplified above, preferredmetallocene compounds as the component (A-2b) in view of excellentmoldability are denoted by “B”. Examples of the compound preferred inview of excellent moldability include:1-indenyl-2-indenyl-dimethylsilylzirconium dichloride; out of compoundsrecited in the above-described literatures such as JP-A-2-76887,JP-A-3-12406, JP-A-3-12407, JP-A-3-12407, JP-A-11-315089,JP-A-2009-143901 and JP-T-2005-507961, zirconium compounds having abridged bis(alkyl-substituted cyclopentadienyl) structure and belongingto formula (2b), where the 2-position of at least one cyclopentadienylring is substituted with an alkyl group and an arbitrary position of atleast another cyclopentadienyl ring is substituted with an alkyl group;out of zirconium compounds having a cyclopentadienyl ring substituted,for example, with an oxygen-containing hydrocarbon group, asulfur-containing hydrocarbon group or a hydrocarbon group-substitutedsilyl group described in JP-T-2002-535339 and the like and belonging toformula (2b), such asdimethylsilylenebis(2-(2-furyl)-3,5-dimethylcyclopentadienyl)zirconiumdichloride, zirconium compounds having a bridged bis(substitutedcyclopentadienyl) structure, where the 2-position of at least onecyclopentadienyl ring is substituted with the above-describedoxygen-containing hydrocarbon group or the like or with an alkyl groupand an arbitrary position of at least another cyclopentadienyl ring issubstituted with the above-described oxygen-containing hydrocarbon groupor the like or with an alkyl group: out of compounds recited in theabove-described literatures such as JP-A-8-59724, JP-A-10-231314,JP-A-2003-105029 and JP-A-2004-352707, silicon-bridged or carbon-bridgedbis(substituted or unsubstituted indenyl)zirconium compounds,silicon-bridged or carbon-bridged bis(substituted or unsubstitutedazulenyl)zirconium compounds and silicon-bridged or carbon-bridged(substituted or unsubstituted indenyl)(substituted or unsubstitutedazulenyl)zirconium compounds belonging to formula (6b) and formula (8b);out of compounds recited in the above-described literatures such asJP-T-2002-535339 and JP-A-2004-352707, zirconium compounds having anindenyl or azulenyl ring substituted, for example, with anoxygen-containing hydrocarbon group, a sulfur-containing hydrocarbongroup or a hydrocarbon group-substituted silyl group and belonging toformula (6b) and formula (8b), where the rings are bridged by a siliconbridging group or a carbon bridging group; and out of compounds recitedin the above-described literatures such as JP-A-6-87922, JP-A-8-92308,JP-A-9-87314, JP-A-7-224079 and JP-A-2005-336092, zirconium compoundsbelonging to formula (7b) and formula (9b), where at least one or moresubstituents which may be the above-described oxygen-containinghydrocarbon group or the like are substituted on cyclopentadienyl ringsconnected by a bridging group and on a cyclopentadienyl ring having aco-ring or the 2-position of at least the cyclopentadienyl ring having aco-ring is substituted with the above-described oxygen-containinghydrocarbon group or the like or with an alkyl group.

Also, in specific compounds exemplified above, more preferred compoundsin view of excellent moldability are denoted by “C”, and other examplesinclude: out of compounds recited in the above-described literaturessuch as JP-A-2-76887, JP-A-3-12406, JP-A-3-12407, JP-A-3-12407,JP-A-11-315089, JP-A-2009-143901 and JP-T-2005-507961, zirconiumcompounds having a bridged bis(alkyl-substituted cyclopentadienyl)structure and belonging to formula (2b), where the 2-position of atleast one cyclopentadienyl ring is substituted with an alkyl group andthe 2- or 5-position of at least another cyclopentadienyl ring issubstituted with an alkyl group: out of zirconium compounds having acyclopentadienyl ring substituted, for example, with anoxygen-containing hydrocarbon group, a sulfur-containing hydrocarbongroup or a hydrocarbon group-substituted silyl group described inJP-T-2002-535339 and the like and belonging to formula (2b), such asdimethylsilylenebis(2-(2-furyl)-3,5-dimethylcyclopentadienyl)zirconiumdichloride, zirconium compounds having a bridged bis(substitutedcyclopentadienyl) structure, where the 2-position of at least onecyclopentadienyl ring is substituted with the above-describedoxygen-containing hydrocarbon group or the like or with an alkyl groupand the 2- or 5-position of at least another cyclopentadienyl ring issubstituted with the above-described oxygen-containing hydrocarbon groupor the like or with an alkyl group; out of compounds recited in theabove-described literatures such as JP-A-8-59724, JP-A-10-231314,JP-A-2003-105029 and JP-A-2004-352707, silicon-bridged or carbon-bridgedbis(substituted or unsubstituted indenyl)zirconium compounds,silicon-bridged or carbon-bridged bis(substituted or unsubstitutedazulenyl)zirconium compounds and silicon-bridged or carbon-bridged(substituted or unsubstituted indenyl)(substituted or unsubstitutedazulenyl)zirconium compounds belonging to formula (6b) and formula (8b),where the 2-position of at least one indenyl or azulenyl ring issubstituted with an alkyl group; out of compounds recited in theabove-described literatures such as JP-T-2002-535339 andJP-A-2004-352707, zirconium compounds having an indenyl or azulenyl ringsubstituted on the 2-position, for example, with an oxygen-containinghydrocarbon group, a sulfur-containing hydrocarbon group or ahydrocarbon group-substituted silyl group and belonging to formula (6b)and formula (8b), where the rings are bridged by a silicon bridginggroup or a carbon bridging group; and out of compounds recited in theabove-described literatures such as JP-A-6-87922, JP-A-8-92308,JP-A-9-87314, JP-A-7-224079 and JP-A-2005-336092, zirconium compoundsbelonging to formula (7b) and formula (9b), where the 2-position of atleast a cyclopentadienyl ring having a co-ring is substituted with theabove-described oxygen-containing hydrocarbon group or the like or withan alkyl group.

Furthermore, in specific compounds exemplified above, still morepreferred compounds in view of excellent moldability are denoted by “D”,and other examples include: out of compounds recited in theabove-described literatures such as JP-A-6-87922, JP-A-8-92308,JP-A-9-87314, JP-A-7-224079 and JP-A-2005-336092, zirconium compoundsbelonging to formula (7b) and formula (9b), where the 2-position of atleast the cyclopentadienyl ring having a co-ring is substituted with theabove-described oxygen-containing hydrocarbon group or the like or withan alkyl group.

In addition, in specific compounds exemplified above, yet still morepreferred compounds in view of excellent moldability are denoted by “E”,and other examples include: out of compounds recited in theabove-described literatures such as JP-A-6-87922, JP-A-8-92308,JP-A-9-87314, JP-A-7-224079 and JP-A-2005-336092, zirconium compoundsbelonging to formula (76) and formula (9b), where the 2-position of atleast the cyclopentadienyl ring having a co-ring is substituted with theabove-described oxygen-containing hydrocarbon group or the like.

Synthesis examples of the metallocene compound as the component (A-2b)according to the present invention are described below, but the presentinvention is not limited to these synthesis methods in particular.

For example, there are a method where an indene compound is lithiated,then reacted with a dichlorosilane compound and subsequently reactedwith cyclopentadienyl lithium to obtain a ligand and the obtained ligandis reacted with a tetrakis(alkylamido)zirconium and then withtrimethylsilyl chloride, and a method where the obtained ligand islithiated and subsequently reacted with zirconium tetrachloride.

IV-2. Olefin Polymerization Catalyst Component Containing Component (Ac)of the Present Invention

A second embodiment of the olefin polymerization catalyst component ofthe present invention contains the component (Ac) defined below as anessential component.

Component (Ac): a metallocene compound represented by the followingformula (1c), where a cyclopentadienyl ring and an indenyl ring arebridged and a specific substituent is substituted on the 4-position ofthe indenyl ring:

[in formula (1c), M^(1c) represents any one transition metal of Ti, Zrand Hf; each of X^(1c) and X^(2c) independently represents a hydrogenatom, a halogen atom, a hydrocarbon group having a carbon number of 1 to20, a hydrocarbon group containing an oxygen atom or a nitrogen atom andhaving a carbon number of 1 to 20, a hydrocarbon group-substituted aminogroup having a carbon number of 1 to 20, or an alkoxy group having acarbon number of 1 to 20: each of Q^(1c) and Q^(2c) independentlyrepresents a carbon atom, a silicon atom or a germanium atom; eachR^(1c) independently represents a hydrogen atom or a hydrocarbon grouphaving a carbon number of 1 to 10 and at least two members out of fourR^(1c) may combine to form a ring together with Q^(1c) and Q^(2c); m^(c)is 0 or 1 and when m^(c) is 0, Q^(1c) is bonded directly to theconjugated 5-membered ring including R^(2c): each of R^(2c) and R^(4c)independently represents a hydrogen atom, a halogen atom, a hydrocarbongroup having a carbon number of 1 to 20, a silicon-containinghydrocarbon group containing from 1 to 6 silicons and having a carbonnumber of 1 to 18, a halogen-containing hydrocarbon group having acarbon number of 1 to 20, a hydrocarbon group containing an oxygen atomand having a carbon number of 1 to 20, or a hydrocarbongroup-substituted silyl group having a carbon number of 1 to 20; andR^(3c) represents a substituted aryl group represented by the followingformula (1-ac)]:

[in formula (1-ac), Y^(1c) represents an atom of Group 14, Group 15 orGroup 16 of the periodic table; each of R^(5c), R^(6c), R^(7c), R^(8c)and R^(9c) independently represents a hydrogen atom, a chlorine atom, abromine atom, a hydrocarbon group having a carbon number of 1 to 20, ahydrocarbon group containing oxygen or nitrogen and having a carbonnumber of 1 to 20, a hydrocarbon group-substituted amino group having acarbon number of 1 to 20, an alkoxy group having a carbon number of 1 to20, a silicon-containing hydrocarbon group containing from 1 to 6silicons and having a carbon number of 1 to 18, a halogen-containinghydrocarbon group having a carbon number of 1 to 20, or a hydrocarbongroup-substituted silyl group having a carbon number of 1 to 20;adjacent groups of R^(5c), R^(6c), R^(7c), R^(8c) and R^(9c) may combinewith each other to form a ring together with the atoms bonded to thesegroups; n^(c) is 0 or 1 and when n^(c) is 0, the substituent R^(5c) isnot present on Y^(1c); and p^(c) is 0 or 1 and when p^(c) is 0, thecarbon atom to which R^(7c) is bonded and the carbon atom to whichR^(9c) is bonded are bonded directly; provided that when Y^(1c) is acarbon atom, at least one of R^(5c), R^(6c), R^(7c), R^(8c) and R^(g9)is not a hydrogen atom].

In formula (1c), M^(1c) of the metallocene compound represents Ti, Zr orHf; M^(1c) of the metallocene compound preferably represents Zr or Hf;and M^(1c) of the metallocene compound more preferably represents Zr.

Each of X^(1c) and X^(2c) independently includes, for example, ahydrogen atom, a chlorine atom, a bromine atom, an iodine atom, a methylgroup, an ethyl group, an n-propyl group, an i-propyl group, an n-butylgroup, an i-butyl group, a tert-butyl group, an n-pentyl group, aneopentyl group, a cyclopentyl group, an n-hexyl group, a cyclohexylgroup, a phenyl group, a benzyl group, a methoxymethyl group, anethoxymethyl group, an n-propoxymethyl group, an i-propoxymethyl group,an n-butoxymethyl group, an i-butoxymethyl group, a tert-butoxymethylgroup, a methoxyethyl group, an ethoxyethyl group, an acetyl group, a1-oxopropyl group, a 1-oxo-n-butyl group, a 2-methyl-1-oxopropyl group,a 2,2-dimethyl-1-oxo-propyl group, a phenylacetyl group, adiphenylacetyl group, a benzoyl group, a 2-methoxyphenyl group, a3-methoxyphenyl group, a 4-methoxyphenyl group, a 2-furyl group, a2-tetrahydrofuryl group, a dimethylaminomethyl group, adiethylaminomethyl group, a di-i-propylaminomethyl group, abis(dimethylamino)methyl group, a bis(di-i-propylamino)methyl group, a(dimethylamino)(phenyl)methyl group, a methylimino group, an ethyliminogroup, a 1-(methylimino)ethyl group, a 1-(phenylimino)ethyl group, a1-[(phenylmethyl)imino]ethyl group, an ethoxy group, an n-propoxy group,an i-propoxy group, an n-butoxy group, an i-butoxy group, a tert-butoxygroup, a phenoxy group, a dimethylamino group, a diethylamino group, adi-n-propylamino group, a di-i-propylamino group, a di-n-butylaminogroup, a di-i-butylamino group, a di-tert-butylamino group, and adiphenylamino group.

Specific preferred examples of X^(1c) and X^(2c) include a chlorineatom, a bromine atom, a methyl group, an n-butyl group, an i-butylgroup, a methoxy group, an ethoxy group, an i-propoxy group, an n-butoxygroup, a phenoxy group, a dimethylamino group, and a di-i-propylaminogroup. Among these specific examples, a chlorine atom, a methyl group,and a dimethylamino group are more preferred.

Each of Q^(1c) and Q^(2c) independently represents a carbon atom, asilicon atom or a germanium atom and is preferably a carbon atom or asilicon atom, more preferably a silicon atom.

Each R^(1c) independently includes, for example, a hydrogen atom, amethyl group, an ethyl group, an n-propyl group, an i-propyl group, ann-butyl group, an i-butyl group, a tert-butyl group, an n-pentyl group,a neopentyl group, a cyclopentyl group, an n-hexyl group, a cyclohexylgroup, and a phenyl group. In the case where R^(1c) forms a ringtogether with Q^(1c) and Q^(2c), examples include a cyclobutylidenegroup, a cyclopentylidene group, a cyclohexylidene group, asilacyclobutyl group, a silacyclopentyl group, and a silacyclohexylgroup.

When Q^(1c) or/and Q^(2c) are a carbon atom, specific preferred examplesof RIe include a hydrogen atom, a methyl group, an ethyl group, a phenylgroup and a cyclobutylidene group, and when Q^(1c) or/and Q^(2c) are asilicon atom, specific preferred examples include a methyl group, anethyl group, a phenyl group and a silacyclobutyl group.

Each of R^(2c) and R^(4c) includes, for example, a hydrogen atom, achlorine atom, a bromine atom, an iodine atom, a methyl group, an ethylgroup, an n-propyl group, an i-propyl group, an n-butyl group, ani-butyl group, a tert-butyl group, an n-pentyl group, a neopentyl group,a cyclopentyl group, an n-hexyl group, a cyclohexyl group, a phenylgroup, a benzyl group, a 2-methylphenyl group, a 3-methylphenyl group, a4-methylphenyl group, a 3,5-dimethylphenyl group, a 4-tert-butylphenylgroup, a 3, 5-di-tert-butylphenyl group, a bis(trimethylsilyl)methylgroup, a bis(tert-butyldimethylsilyl)methyl group, a bromomethyl group,a chloromethyl group, a 2-chloroethyl group, a 2-bromoethyl group, a2-bromopropyl group, a 3-bromopropyl group, a 2-bromocyclopentyl group,a 2,3-dibromocyclopentyl group, a 2-bromo-3-iodocyclopentyl group, a2,3-dibromocyclohexyl group, a 2-chloro-3-iodocyclohexyl group, a2-chlorophenyl group, a 4-chlorophenyl group, a2,3,4,5,6-pentafluorophenyl group, a 4-trifluoromethylphenyl group, afuryl group, a tetrahydrofuryl group, a 2-methylfuryl group, atrimethylsilyl group, a tri-tert-butylsilyl group, adi-tert-butylmethylsilyl group, a tert-butyldimethylsilyl group, atriphenylsilyl group, a diphenylmethylsilyl group, and aphenyldimethylsilyl group.

Each of R^(2c) and R^(4c) is preferably a hydrocarbon group having acarbon number of 1 to 20, a silicon-containing hydrocarbon groupcontaining from 1 to 6 silicons and having a carbon number of 1 to 18, ahalogen-containing hydrocarbon group having a carbon number of 1 to 20,a hydrocarbon group containing an oxygen atom and having a carbon numberof 1 to 20, or a hydrocarbon group-substituted silyl group having acarbon number of 1 to 20, because the polymerization activity becomeshigh in particular.

Specific preferred examples of R^(2c) and R^(4c) include a hydrogenatom, a methyl group, an ethyl group, an n-propyl group, an i-propylgroup, an n-butyl group, a tert-butyl group, an n-pentyl group, ann-hexyl group, a cyclohexyl group, a phenyl group, a 2-methylfurylgroup, and a trimethylsilyl group. Among these specific examples, ahydrogen atom, a methyl group, an n-butyl group, a tert-butyl group, aphenyl group and a trimethylsilyl group are more preferred, and ahydrogen atom, a methyl group, a tert-butyl group, a phenyl group and atrimethylsilyl group are still more preferred.

The substituent R^(13c) represents a substituted aryl group having astructure represented by formula (1-ac), preferably a Ph group having aspecific substituent, furyl groups, or thienyl groups. Specific examplesinclude a 4-trimethylsilylphenyl group, a4-(tert-butyldimethylsilyl)phenyl group, a4-(3,5-bistrimethylsilyl)phenyl group, a 4-chlorophenyl group, a4-bromophenyl group, a 3,5-dichlorophenyl group, a 2,4,6-trichlorophenylgroup, a 4-methoxyphenyl group, a 4-ethoxyphenyl group, a4-isopropoxyphenyl group, a 4-n-butoxyphenyl group, a 2-furyl group, a2-(5-methyl)furyl group, a 2-(5-tert-butyl)furyl group, a2-(5-trimethylsilyl)furyl group, a 2-(2,3-dimethyl)furyl group, a2-benzofuryl group, a 2-thienyl group, a 2-(5-methyl)thienyl group, a2-(5-tert-butyl)thienyl group, a 2-(5-trimethylsilyl)thienyl group, anda 2-(2,3-dimethyl)thienyl group.

Also, in formula (1), m^(c) is 0 or 1 and when m^(c) is 0, Q^(1c) isbonded directly to the conjugated 5-membered ring including R^(2c).

The metallocene compound of the present invention is preferably acompound represented by the following formula (2c):

In the metallocene compound represented by formula (2c), for M^(1c),X^(1c), X^(2c), Q^(1c), R^(1c), R^(2c) and R^(4c), the same structuresas the atom and the group described above in the metallocene compoundrepresented by formula (1c) may be selected. Also, for R^(10c), the samestructure as the atom or group of R^(5c), R^(6c), R^(7c), R^(8c) andR^(9c) described above in the metallocene compound represented byformula (1c) may be selected.

As the metallocene compound of the present invention, a compoundrepresented by the following formula (3c) is also preferred similarly toformula (2c):

In the metallocene compound represented by formula (3c), for M^(1c),X^(1c), X^(2c), Q^(1c), R^(1c), R^(2c) and R^(4c), the same structuresas the atom and the group described above in the metallocene compoundrepresented by formula (1c) may be selected. Also, for R^(12c), R^(13x)and R^(14c), the same structures as the atom and the group of R^(5c),R^(6c), R^(7c), R^(8c) and R^(9c) described above in the metallocenecompound represented by formula (1c) may be selected. Z1c represents anoxygen atom or a sulfur atom.

Specific examples of the metallocene compound represented by formula(3c) are shown in Tables c-1 to c-5 by using formula (4c), but thepresent invention is not limited thereto.

TABLE c-1 R^(3c) = Si-Substituted Phenyl Group X^(1c), No. M^(1c) X^(2c)Q^(1c) R^(3c)  1c Zr Cl Me₂Si 4-(trimethylsilyl)-phenyl  2c Zr Br Me₂Si4-(trimethylsilyl)-phenyl  3c Zr Me Me₂Si 4-(trimethylsilyl)-phenyl  4cZr Ph Me₂Si 4-(trimethylsilyl)-phenyl  5c Zr Cl Et₂Si4-(trimethylsilyl)-phenyl  6c Zr Cl Ph₂Si 4-(trimethylsilyl)-phenyl  7cZr Cl silacyclobutyl 4-(trimethylsilyl)-phenyl  8c Zr Cl silacyclohexyl4-(trimethylsilyl)-phenyl  9c Zr Cl Me₂C 4-(trimethylsilyl)-phenyl 10cZr Cl Ph₂C 4-(trimethylsilyl)-phenyl 11c Zr Cl Me₂Ge4-(trimethylsilyl)-phenyl 12c Zr Cl Me₂Si 4-(triethylsilyl)-phenyl 13cZr Cl Me₂Si 4-(tri-n-propylsilyl)-phenyl 14c Zr Cl Me₂Si4-(tri-i-propylsilyl)-phenyl 15c Zr Cl Me₂Si 4-(tri-n-butylsilyl)-phenyl16c Zr Cl Me₂Si 4-(tri-i-butylsilyl)-phenyl 17c Zr Cl Me₂Si4-(tri-n-pentylsilyl)-phenyl 18c Zr Cl Me₂Si 4-(tri-n-hexylsilyl)-phenyl19c Zr Cl Me₂Si 4-(trivinylsilyl)-phenyl 20c Zr Cl Me₂Si4-(triphenylsilyl)-phenyl 21c Zr Cl Me₂Si 4-(tribenzylsilyl)-phenyl 22cZr Cl Me₂Si 4-(t-butyldimethylsilyl)-phenyl 23c Zr Cl Me₂Si4-(di-tert-butylmethylsilyl)- phenyl 24c Zr Cl Me₂Si4-(dimethylethylsilyl)-phenyl 25c Zr Cl Me₂Si4-(methyldiethylsilyl)-phenyl 26c Zr Cl Me₂Si4-(dimethyl-n-propylsilyl)-phenyl 27c Zr Cl Me₂Si4-(methyl-di-n-propylsilyl)-phenyl 28c Zr Cl Me₂Si4-(dimethyl-i-propylsilyl)-phenyl 29c Zr Cl Me₂Si4-(methyl-di-i-propylsilyl)-phenyl 30c Zr Cl Me₂Si4-(dimethyl-n-butylsilyl)-phenyl

TABLE c-2 R^(3c) = Si-Substituted Phenyl Group (continued) X^(1c), No.M^(1c) X^(2c) Q^(1c) R^(3c) 31c Zr Cl Me₂Si4-(methyl-di-n-butylsilyl)-phenyl 32c Zr Cl Me₂Si4-(dimethyl-n-pentylsilyl)-phenyl 33c Zr Cl Me₂Si4-(methyl-di-n-pentylsilyl)-phenyl 34c Zr Cl Me₂Si4-(dimethylbenzylsilyl)-phenyl 35c Zr Cl Me₂Si4-(methyldibenzylsilyl)-phenyl 36c Zr Cl Me₂Si4-(dimethylvinylsilyl)-phenyl 37c Zr Cl Me₂Si4-(methyldivinylsilyl)-phenyl 38c Zr Cl Me₂Si4-(dimethylmethoxysilyl)-phenyl 39c Zr Cl Me₂Si4-(methyldimethoxysilyl)-phenyl 40c Zr Cl Me₂Si4-(trimethoxysilyl)-phenyl 41c Zr Cl Me₂Si4-(ethoxydimethylsilyl)-phenyl 42c Zr Cl Me₂Si4-(diethoxymethylsilyl)-phenyl 43c Zr Cl Me₂Si 4-(triethoxysilyl)-phenyl44c Zr Cl Me₂Si 4-(dimethylphenylsilyl)-phenyl 45c Zr Cl Me₂Si4-(methyldiphenylsilyl)-phenyl 46c Zr Cl Me₂Si4-(diethylphenylsilyl)-phenyl 47c Zr Cl Me₂Si4-(ethyldiphenylsilyl)-phenyl 48c Zr Cl Me₂Si4-(methoxydiphenylsilyl)-phenyl 49c Zr Cl Me₂Si4-(dimethoxyphenylsilyl)-phenyl 50c Zr Cl Me₂Si4-(ethoxydiphenylsilyl)-phenyl 51c Zr Cl Me₂Si4-(diethoxyphenylsilyl)-phenyl 52c Zr Cl Me₂Si4-(allyldimethylsilyl)-phenyl 53c Zr Cl Me₂Si4-(diallylmethylsilyl)-phenyl 54c Zr Cl Me₂Si 4-(triallylsilyl)-phenyl

TABLE c-3 R^(3c) = Furyl or Thienyl Substituent No. M^(1c) X^(1c),X^(2c) Q^(1c) R^(3c) 55c Zr Cl Me₂Si 2-furyl 56c Zr Cl Me₂Si5-methyl-2-furyl 57c Zr Br Me₂Si 5-methyl-2-furyl 58c Zr Me Me₂Si5-methyl-2-furyl 59c Zr Ph Me₂Si 5-methyl-2-furyl 60c Zr Cl Et₂Si5-methyl-2-furyl 61c Zr Cl Ph₂Si 5-methyl-2-furyl 62c Zr Clsilacyclobutyl 5-methyl-2-furyl 63c Zr Cl silacyclohexyl5-methyl-2-furyl 64c Zr Cl Me₂C 5-methyl-2-furyl 65c Zr Cl Ph₂C5-methyl-2-furyl 66c Zr Cl Me₂Ge 5-methyl-2-furyl 67c Zr Cl Me₂Si5-ethyl-2-furyl 68c Zr Cl Me₂Si 5-n-propyl-2-furyl 69c Zr Cl Me₂Si5-i-propyl-2-furyl 70c Zr Cl Me₂Si 5-n-butyl-2-furyl 71c Zr Cl Me₂Si5-i-butyl-2-furyl 72c Zr Cl Me₂Si 5-tert-butyl-2-furyl 73c Zr Cl Me₂Si5-trimethylsilyl-2-furyl 74c Zr Cl Me₂Si 5-triethylsilyl-2-furyl 75c ZrCl Me₂Si 5-phenyl-2-furyl 76c Zr Cl Me₂Si 5-tolyl-2-furyl 77c Zr ClMe₂Si 5-fluorophenyl-2-furyl 78c Zr Cl Me₂Si 5-chlorophenyl-2-furyl 79cZr Cl Me₂Si 4,5-dimethyl-2-furyl 80c Zr Cl Me₂Si 2-benzofuryl 81c Zr ClMe₂Si 2-thienyl 82c Zr Cl Me₂Si 5-methyl-2-thienyl 83c Zr Cl Me₂Si5-ethyl-2-thienyl 84c Zr Cl Me₂Si 5-n-propyl-2-thienyl 85c Zr Cl Me₂Si5-i-propyl-2-thienyl 86c Zr Cl Me₂Si 5-tert-butyl-2-thienyl 87c Zr ClMe₂Si 5-trimethylsilyl-2-thienyl 88c Zr Cl Me₂Si5-triethylsilyl-2-thienyl 89c Zr Cl Me₂Si 5-phenyl-2-thienyl 90c Zr ClMe₂Si 5-tolyl-2-thienyl 91c Zr Cl Me₂Si 5-fluorophenyl-2-thienyl 92c ZrCl Me₂Si 5-chlorophenyl-2-thienyl 93c Zr Cl Me₂Si 4,5-dimethyl-2-thienyl94c Zr Cl Me₂Si 2-benzothienyl

TABLE c-4 R^(3c) = Halogen-Substituted Phenyl Group No. M^(1c) X^(1c),X^(2c) Q^(1c) R^(3c)  95c Zr Cl Me₂Si 4-chloro-phenyl  96c Zr Br Me₂Si4-chloro-phenyl  97c Zr Me Me₂Si 4-chloro-phenyl  98c Zr Ph Me₂Si4-chloro-phenyl  99c Zr Cl Et₂Si 4-chloro-phenyl 100c Zr Cl Ph₂Si4-chloro-phenyl 101c Zr Cl silacyclobutyl 4-chloro-phenyl 102c Zr Clsilacyclohexyl 4-chloro-phenyl 103c Zr Cl Me₂C 4-chloro-phenyl 104c ZrCl Ph₂C 4-chloro-phenyl 105c Zr Cl Me₂Ge 4-chloro-phenyl 106c Zr ClMe₂Si 4-bromo-phenyl 107c Zr Cl Me₂Si 4-iodo-phenyl 108c Zr Cl Me₂Si3,5-dichloro-phenyl 109c Zr Cl Me₂Si 3,5-dibromo-phenyl 110c Zr Cl Me₂Si2,6-dichloro-phenyl 111c Zr Cl Me₂Si 2,6-dibromo-phenyl 112c Zr Cl Me₂Si2,4,6-trichloro-phenyl 113c Zr Cl Me₂Si 2,4,6-tribromo-phenyl 114c Zr ClMe₂Si 2,3,4,5,6-pentachloro-phenyl 115c Zr Cl Me₂Si2,3,4,5,6-pentabromo-phenyl

TABLE c-5 R^(3c) = Alkoxy-Substituted Phenyl Group X^(1c), No. M^(1c)X^(2c) Q^(1c) R^(3c) 116c Zr Cl Me₂Si 4-methoxy-phenyl 117c Zr Br Me₂Si4-methoxy-phenyl 118c Zr Me Me₂Si 4-methoxy-phenyl 119c Zr Ph Me₂Si4-methoxy-phenyl 120c Zr Cl Et₂Si 4-methoxy-phenyl 121c Zr Cl Ph₂Si4-methoxy-phenyl 122c Zr Cl silacyclobutyl 4-methoxy-phenyl 123c Zr Clsilacyclohexyl 4-methoxy-phenyl 124c Zr Cl Me₂C 4-methoxy-phenyl 125c ZrCl Ph₂C 4-methoxy-phenyl 126c Zr Cl Me₂Ge 4-methoxy-phenyl 127c Zr ClMe₂Si 4-ethoxy-phenyl 128c Zr Cl Me₂Si 4-n-propoxy-phenyl 129c Zr ClMe₂Si 4-i-propoxy-phenyl 130c Zr Cl Me₂Si 4-n-butoxy-phenyl 131c Zr ClMe₂Si 4-i-butoxy-phenyl 132c Zr Cl Me₂Si 4-tert-butoxy-phenyl 133c Zr ClMe₂Si 4-phenoxy-phenyl 134c Zr Cl Me₂Si4-(2,4,6-trimethylphenoxy)-phenyl 135c Zr Cl Me₂Si4-(2,6-di-i-propylphenoxy)-phenyl 136c Zr Cl Me₂Si4-(2,6-di-tert-butylphenoxy)- phenyl 137c Zr Cl Me₂Si3,5-dimethoxy-phenyl 138c Zr Cl Me₂Si 2,4,6-trimethoxy-phenyl 139c Zr ClMe₂Si 4-thiomethoxy-phenyl 140c Zr Cl Me₂Si 4-dimethylamino-phenyl 141cZr Cl Me₂Si 4-diethylamino-phenyl 142c Zr Cl Me₂Si4-trimethylsilyloxy-phenyl 143c Zr Cl Me₂Si 4-triethylsilyloxy-phenyl

For example, compounds where zirconium of the compounds above isreplaced by titanium or hafnium are also preferred.

Among specific compounds exemplified above, preferred metallocenecompounds as the essential component (Ac) are described below. Thecompounds include, for example, 1c-10c, 12c to 65c, 67c to 80c, and 95cto 143c in Tables c-1 to c-5.

Preferred metallocene compounds also include, for example, compoundswhere zirconium of the compounds above is replaced by titanium orhafnium.

Among specific compounds exemplified above, more preferred metallocenecompounds as the essential component (Ac) are described below. Thecompounds include, for example, 1c-4c, 7c, 8c, 12c to 38c, 44c to 47c,52c to 59c, 62c, 63c, 67c to 80c, 116c to 123c, 127c to 136c, 142c, and143c in Tables c-1 to c-5.

Preferred metallocene compounds also include, for example, compoundswhere zirconium of the compounds above is replaced by titanium orhafnium.

Furthermore, among specific compounds exemplified above, in terms ofhigh polymerization activity, still more preferred metallocene compoundsas the essential component (Ac) are described below. The compoundsinclude, for example, 1c-8c, 12c to 38c, 44c to 47c, 52c to 63c, 67c to80c, 116c to 123c, 127c to 136c, 142c, and 143c in Tables c-1 to c-5.

Preferred metallocene compounds also include, for example, compoundswhere zirconium of the compounds above is replaced by titanium orhafnium.

In addition, among specific compounds exemplified above, in terms ofexcellent moldability, still more preferred metallocene compounds as theessential component (Ac) are described below. The compounds include, forexample, 1c-4c, 7c to 10c, 12c to 59c, 62c to 65c, 67c to 80c, and 95cto 143c in Tables c-1 to c-5.

Preferred metallocene compounds also include, for example, compoundswhere zirconium of the compounds above is replaced by titanium orhafnium.

In the case of using these metallocene compounds as the component (Ac),two or more thereof may be also used.

Synthesis Method of Metallocene Compound

The metallocene compound of the present invention can be synthesized byan arbitrary method utilizing a form of a substituent or a bond. Oneexample of the representative synthesis route is shown below.

In the synthesis route above, a coupling reaction of Compound 1 and a4-trimethylsilylphenylboronic acid is performed in the presence of apalladium catalyst to obtain Compound 2. Compound 2 is anionized with anequivalent of n-butyllithium or the like and then reacted with an excessamount of dimethyldichlorosilane, and thereafter, unreacteddimethyldichlorosilane is removed by distillation to obtain Compound 3.Compound 3 obtained is reacted with sodium cyclopentadienylide to obtainCompound 4, and Compound 4 is dianionized with 2 equivalents ofn-butyllithium or the like and then reacted with zirconium tetrachlorideto obtain Compound 5. The metallocene compound having introducedthereinto a substituent can be synthesized by using a corresponding rawmaterial for substitution, and a corresponding substituent can beintroduced into the 4-position of the indenyl ring by using acorresponding boronic acid, for example, 4-chlorophenylboronic acid,4-methoxyphenylboronic acid, 5-methylfuryl-2-boronic acid,4,5-dimethylfuryl-2-boronic acid or 2-thienylboronic acid, in place of4-trimethylsilylphenylboronic acid.

IV-3. Olefin Polymerization Catalyst of the Present Invention ContainingOlefin Polymerization Catalyst Components (A-1b) and (A-2b) of thePresent Invention or Olefin Polymerization Catalyst of the PresentInvention Containing Olefin Polymerization Catalyst Component (Ac) ofthe Present Invention

The olefin polymerization catalyst of the present invention comprisesthe following components (A) and (B) and, if desired, further containsthe component (C):

component (A): the olefin polymerization catalyst component of thepresent invention specified above,

component (B): a compound capable of reacting with the component (A) toproduce a cationic metallocene compound, and

component (C): a microparticle support.

The olefin polymerization catalyst of the present invention is describedbelow item by item (hereinafter, the olefin polymerization catalystcomponent of the present invention is sometimes referred to as component(A) or simply as A).

IV-3(1). Component (B)

The olefin polymerization catalyst of the present invention contains, asthe component (B), a compound capable of reacting with the metallocenecompound of the component (A) to produce a cationic metallocene compound(hereinafter, sometimes referred to as component (B) or simply as B) andpreferably contains the component (B) and a microparticle support(preferred component (C); hereinafter sometimes simply referred to asC).

One of the compounds (B) capable of reacting with the metallocenecompound (A) to produce a cationic metallocene compound is anorganoaluminum oxy compound.

The organoaluminum oxy compound has an Al—O—Al bond in the molecule, andthe number of bonds is usually from 1 to 100, preferably from 1 to 50.Such an organoaluminum oxy compound is a product obtained usually byreacting an organoaluminum compound and water.

The reaction of an organoaluminum and water is usually performed in aninert hydrocarbon (solvent). As the inert hydrocarbon, an aliphatichydrocarbon, an alicyclic hydrocarbon and an aromatic hydrocarbon, suchas pentane, hexane, heptane, cyclohexane, methylcyclohexane, benzene,toluene and xylene, can be used, but it is preferred to use an aliphatichydrocarbon or an aromatic hydrocarbon.

As the organoaluminum compound used for preparing the organoaluminum oxycompound, any of compounds represented by the following formula (11b)may be usable, but a trialkylaluminum is preferably used.

R^(23b) _(t)AlX^(21b) _(3-t)  formula (11b)

(wherein R^(23b) represents a hydrocarbon group having a carbon numberof 1 to 18, preferably from 1 to 12, such as alkyl group, alkenyl group,aryl group and aralkyl group, X^(21b) represents a hydrogen atom or ahalogen atom, and t represents an integer of 1≦t≦3).

The alkyl group of the trialkylaluminum may be any of a methyl group, anethyl group, a propyl group, an isopropyl group, a butyl group, anisobutyl group, a pentyl group, a hexyl group, an octyl group, a decylgroup, a dodecyl group and the like, but among others, is preferably amethyl group.

Two or more of the organoaluminum compounds above can be also mixed andused.

The ratio between water and the organoaluminum compound in the reaction(molar ratio of water/Al) is preferably from 0.25/1 to 1.2/1, morepreferably from 0.5/1 to 1/1. The reaction temperature is usually from−70 to 100° C., preferably from −20 to 20° C. The reaction time isselected in the range of usually from 5 minutes to 24 hours, preferablyfrom 10 minutes to 5 hours. As the water required in the reaction, notonly mere water but also crystal water contained, for example, in coppersulfate hydrate or aluminum sulfate hydrate or a component capable ofproducing water in the reaction system can be utilized.

Incidentally, out of the organoaluminum oxy compounds described above,those obtained by reacting an alkylaluminum with water is usually calledaluminoxane and among others, methylaluminoxane (encompassing thosesubstantially composed of methylaluminoxane (MAO)) is preferred as theorganoaluminum oxy compound.

Of course, as the organoaluminum oxy compound, two or more of theorganoaluminum oxy compounds described above may be used in combination.Also, the organoaluminum oxy compound may be used as a solution bydissolving or dispersing it in the above-described inert hydrocarbonsolvent.

When an organoaluminum oxy compound is used as the component (B) of theolefin polymerization catalyst component of the present invention, thestrain hardening (λmax) of the obtained ethylene-based polymer becomeshigh or Mz/Mw (where Mz is a Z average molecular weight measured by GPCand Mw is a weight average molecular weight measured by the same method)indicative of the high-molecular-weight component content becomes largeand in turn, the moldability is advantageously more improved.

Other specific examples of the compound (B) capable of reacting with themetallocene compound (A) to form a cationic metallocene compound includea borane compound and a borate compound.

More specifically, examples of the borane compound includetriphenylborane, tri(o-tolyl)borane, tri(p-tolyl)borane,tri(m-tolyl)borane, tri(o-fluorophenyl)borane,tris(p-fluorophenyl)borane, tris(m-fluorophenyl)borane,tris(2,5-difluorophenyl)borane, tris(3,5-difluorophenyl)borane,tris(4-trifluoromethylphenyl)borane,tris(3,5-ditrifluoromethylphenyl)borane,tris(2,6-ditrifluoromethylphenyl)borane, tris(pentafluorophenyl)borane,tris(perfluoronaphthyl)borane, tris(perfluorobiphenyl),tris(perfluoroanthryl)borane and tris(perfluorobinaphthyl)borane.

Among these compounds, preferred aretris(3,5-ditrifluoromethylphenyl)borane,tris(2,6-ditrifluoromethylphenyl)borane, tris(pentafluorophenyl)borane,tris(perfluoronaphthyl)borane, tris(perfluorobiphenyl)borane,tris(perfluoroanthryl)borane and tris(perfluorobinaphthyl)borane, andmore preferred are tris(2,6-ditrifluoromethylphenyl)borane,tris(pentafluorophenyl)borane, tris(perfluoronaphthyl)borane andtris(perfluorobiphenyl)borane.

A first example of the borate compound is specifically a compoundrepresented by the following formula (12b):

[L^(1b)-H]⁺[BR^(24b)R^(25b)X^(31b)X^(32b)]⁻  formula (12b)

In formula (12b), L^(1b) is a neutral Lewis base, H is a hydrogen atom,and [L^(1b)-H] is a Broensted acid such as ammonium, anilinium andphosphonium.

Examples of the ammonium include a trialkyl-substituted ammonium such astrimethylammonium, triethylammonium, tripropylammonium, tributylammoniumand tri(n-butyl)ammonium, and a dialkylammonium such asdi(n-propyl)ammonium and dicyclohexylammonium.

Examples of the anilinium include an N,N-dialkylanilinium such asN,N-dimethylanilinium, N,N-diethylanilinium andN,N-2,4,6-pentamethylanilinium.

Furthermore, examples of the phosphonium include a triarylphosphoniumand a trialkylphosphonium, such as triphenylphosphonium,tributylphosphonium, tri(methylphenyl)phosphonium andtri(dimethylphenyl)phosphonium.

In formula (12b), each of R^(24b) and R^(25b) is independently the sameor different aromatic or substituted aromatic hydrocarbon group having acarbon number of 6 to 20, preferably from 6 to 16, and these groups maybe connected with each other through a bridging group. The substituentof the substituted aromatic hydrocarbon group is preferably an alkylgroup typified by a methyl group, an ethyl group, a propyl group and anisopropyl group, or a halogen atom such as fluorine, chlorine, bromineand iodine.

Furthermore, each of X^(31b) and X³² is independently a hydride group, ahalide group, a hydrocarbon group having a carbon number of 1 to 20, ora substituted hydrocarbon group having a carbon number of 1 to 20, inwhich one or more hydrogen atoms are substituted for by a halogen atom.

Specific examples of the compound represented by formula (12b) includetributylammoniumtetra(pentafluorophenyl)borate,tributylammoniumtetra(2,6-ditrifluoromethylphenyl)borate,tributylammoniumtetra(3,5-ditrifluoromethylphenyl)borate,tributylammoniumtetra(2,6-difluorophenyl)borate,tributylammoniumtetra(perfluoronaphthyl)borate,dimethylaniliniumtetra(pentafluoronaphthyl)borate,dimethylaniliniumtetra(2,6-ditrifluoromethylphenyl)borate,dimethylaniliniumtetra(3,5-ditrifluoromethylphenyl)borate,dimnethylaniliniumtetra(2,6-difluorophenyl)borate,dimethylaniliniiuntetra(perfluoronaphdthyl)borate,triphenylphosphoniumtetra(pentafluorophenyl)borate,triphenylphosphoniumtetra(2,6-ditrifluoromethylphenyl)borate,triphenylphosphoniumtetra(3,5-ditrifluoromethylphenyl)borate,triphenylphosphoniumtetra(2,6-difluorophenyl)borate,triphenylphosphoniumtetra(perfluoronaphthyl)borate,trimethylammoniumtetra(2,6-ditrifluoromethylphenyl)borate,triethylammoniumtetra(pentafluorophenyl)borate,triethylanmmoniumtetra(2,6-ditrifluoromethylphenyl)borate,triethylammoniumtetra(perfluoronaphthyl)borate,tripropylammoniumtetra(pentafluorophenyl)borate,tripropylammoniumtetra(2,6-ditrifluoromethylphenyl)borate,tripropylanunoniumtetra(perfluoronaphthyl)borate,di(1-propyl)ammoniumtetra(pentafluorophenyl)borate, anddicyclohexylammoniumtetraphenylborate.

Among these, preferred aretributylammnoniumtetra(pentafluorophenyl)borate,tributylammoniumtetra(2,6-ditrifluoromethylphenyl)borate,tributylanummoniumtetra(3,5-ditrifluoromethylphenyl)borate,tributylammoniumtetra(perfluoronaphthyl)borate,dimethylaniliniumtetra(pentafluoropheuyl)borate,dimethylanilinumtetra(2,6-ditrifluoromethylphenyl)borate,dimethylaniliniumtetra(3,5-ditrifluoromethylphenyl)borate anddimethylaniliniumtetra(perfluoronaphthyl)borate.

A second example of the borate compound is represented by the followingformula (13b):

[L^(2b)]⁺[BR^(26b)R^(27b)X^(41b)X^(42b)]  formula (13b)

In formula (13b). L^(2b) includes, for example, a carbo-cation, a methylcation, an ethyl cation, a propyl cation, an isopropyl cation, a butylcation, an isobutyl cation, a tert-butyl cation, a pentyl cation, atropinium cation, a benzyl cation, a trityl cation, a sodium cation, anda proton. R^(26b), R^(27b), X^(41b) and X^(42b) have the samedefinitions as in formula (12b).

Specific examples of the compound above include trityltetraphenylborate,trityltetra(o-tolyl)borate, trityltetra(p-tolyl)borate,trityltetra(m-tolyl)borate, trityltetra(o-fluorophenyl)borate,trityltetra(p-fluorophenyl)borate, trityltetra(m-fluorophenyl)borate,trityltetra(3,5-difluorophenyl)borate,trityltetra(pentafluorophenyl)borate,trityltetra(2,6-ditrifluoromethylphenyl)borate,trityltetra(3,5-ditrifluoromethylpheuyl)borate,trityltetra(perfluoronaphthyl)borate, tropinium-tetraphenylborate,tropinium-tetra(o-tolyl)borate, tropinium-tetra(p-tolyl)borate,tropinium-tetra(m-tolyl)borate, tropinium-tetra(o-fluorophenyl)borate,tropinium-tetra(p-fluorophenyl)borate,tropinium-tetra(m-fluorophenyl)borate,tropinium-tetra(3,5-difluorophenyl)borate,tropinium-tetra(pentafluorophenyl)borate,tropinium-tetra(2,6-ditrifluoromethylphenyl)borate,tropinium-tetra(3,5-ditrifluoromethylphenyl)borate,tropinium-tetra(perfluoronaphthyl)borate, NaBPh₄, NaB(o-CH₃-Ph)₄,NaB(p-CH₃-Ph)₄, NaB(m-CH₃-Ph)₄, NaB(o-F-Ph)₄, NaB(p-F-Ph)₄,NaB(m-F-Ph)₄, NaB(3,5-F₂-Ph)₄, NaB(C₆F₅)₄, NaB(2,6-(CF₃)₂-Ph)₄,NaB(3,5-(CF₃)₂-Ph)₄, NaB(C₁₀F₇)₄, HBPh₄.2-diethyl ether,H⁺B(3,5-F₂-Ph)₄.2-diethyl ether, H⁺B(C₆F₅)₄ ⁻.2-diethyl ether,H⁺B(2,6-(CF₃)-Ph)₄.2-diethyl ether, H⁺B(3,5-(CF₃)-Ph)₄.2-diethyl ether,and H⁺B(C₁₀H₇)₄.2-diethyl ether.

Among these, preferred are trityltetra(pentafluorophenyl)borate,trityltetra(2,6-ditrifluoromethylphenyl)borate,trityltetra(3,5-ditrifluoromethylphenyl)borate,trityltetra(perfluoronaphthyl)borate,tropinium-tetra(pentafluorophenyl)borate,tropinium-tetra(2,6-ditrifluoromethylphenyl)borate,tropinium-tetra(3,5-ditrifluoromethylphenyl)borate,tropinium-tetra(perfluoronaphthyl)borate, NaB(C₆F₅)₄,NaB(2,6-(CF₃)₂-Ph)₄, NaB(3,5-(CF₃)₂-Ph)₄, NaB(C₁₀F₇)₄, H⁺B(C₆F₅)₄⁻.2-diethyl ether, H⁺B(2,6-(CF₃)₂-Ph)₄.2-diethyl ether,H⁺B(3,5-(CF₃)₂-Ph)₄.2-diethyl ether and H⁺B(C₁₀H₇)₄.2-diethyl-ether.

Among these, still more preferred aretrityltetra(pentafluorophenyl)borate,trityltetra(2,6-ditrifluoromethylphenyl)borate,tropinium-tetra(pentafluorophenyl)borate,tropinium-tetra(2,6-ditrifluoromethylphenyl)borate, NaB(C₆F₅)₄,NaB(2,6-(CF₃)₂-Ph)₄, H⁺B(C₆F₅)₄ ⁻.2-diethyl ether,H⁺B(2,6-(CF₃)₂-Ph)₄.2-diethyl ether, H⁺B(3,5-(CF₃)₂-Ph)₄.2-diethyl etherand H⁺B(C₁₀H₇)₄.2-diethyl ether.

When a borane compound or a borate compound is used as the catalystcomponent (B), the polymerization activity or copolymerizability isincreased and therefore, the productivity of an ethylene-based polymerhaving a long-chain branch is enhanced.

Also, a mixture of the above-described organoaluminum oxy compound andthe above-described borane or borate compound may be also used as thecomponent (B) of the olefin polymerization catalyst. Furthermore, two ormore of those borane or borate compounds may be mixed and used.

As other specific examples of the compound (B) capable of reacting withthe metallocene compound (A) to form a cationic metallocene compound, acompound having the same action as the above-described organoaluminumoxy compound or the above-described borane or borate compound, such asclay, clay mineral, ion-exchanging layered compound and inorganicsilicate described, for example, in JP-A-8-127613 and solid oxidecompound described, for example, JP-T-2002-515522, may be also used inthe same manner.

IV-3(2). Preferred Component (C)

The microparticle support as the preferred component (C) of the olefinpolymerization catalyst of the present invention includes an inorganicsupport, a particulate polymer support, and a mixture thereof. As theinorganic support, a metal, a metallic oxide, a metallic chloride, ametallic carbonate, a carbonaceous substance, or a mixture thereof canbe used.

Preferred examples of the metal that can be used for the inorganicsupport include iron, aluminum, and nickel.

The metallic oxide includes a single oxide or a composite oxide ofelements belonging to Groups 1 to 14 of the periodic table, and examplesthereof include various natural or synthetic, single or composite oxidessuch as SiO₂, Al₂O₃, MgO, CaO, B₂O₃, TiO₂, ZrO₂, Fe₂O₃, Al₂O₃.MgO,Al₂O₃.CaO, Al₂O₃.SiO₂, Al₂O₃.MgO.CaO, Al₂O₃.MgO.SiO₂, Al₂O₃.CuO,Al₂O₃.Fe₂O₃, Al₂O₃.NiO and SiO₂.MgO. Here, these formulae are not amolecular formula but indicate only a composition, and the structure andcomponent ratio of the composite oxide for use in the present inventionare not particularly limited.

Also, the metallic oxide for use in the present invention may haveabsorbed a small amount of water or may contain a small amount ofimpurities.

As the metallic chloride, for example, a chloride of an alkali metal oran alkaline earth metal is preferred, and specifically, MgCl₂, CaCl₂ andthe like are suited in particular.

As the metallic carbonate, a carbonate of an alkali metal or an alkalineearth metal is preferred, and specific examples thereof includemagnesium carbonate, calcium carbonate, and barium carbonate.

The carbonaceous substance includes, for example, carbon black andactivated carbon.

All of these inorganic supports can be suitably used in the presentinvention, but among others, use of a metallic oxide, silica, alumina orthe like is preferred.

Such an in organic support is preferably used by burning it in an air oran inert gas such as nitrogen or argon at a temperature of usually from200 to 800° C., preferably from 400 to 600° C., thereby adjusting theamount of a surface hydroxyl group to be from 0.8 to 1.5 mmol/g.

The property of the inorganic support is not particularly limited, butit is usually preferred to use an inorganic support having an averageparticle diameter of 5 to 200 μm, preferably from 10 to 150 μm, anaverage pore diameter of 20 to 1,000 Å, preferably from 50 to 500 Å, aspecific surface area of 150 to 1,000 m²/g, preferably from 200 to 700m²/g, a pore volume of 0.3 to 2.5 cm³/g, preferably from 0.5 to 2.0cm³/g, and an apparent specific gravity of 0.20 to 0.50 g/cm³,preferably from 0.25 to 0.45 g/cm³.

The inorganic support may be of course used as it is but may be usedafter applying a preliminary treatment of contacting such a support withan organoaluminum compound such as trimethylaluminum, triethylaluminum,triisobutylaluminum, trihexylaluminum, tripropylaluminum,tributylaluminum, trioctylaluminum, tridecylaluminum anddiisobutylaluminum hydride, or an organoaluminum oxy compound containingan Al—O—Al bond.

In addition, a powder of the component (A) or component (B) can be alsoused as the microparticle support.

IV-3(3). Preparation Method of Olefin Polymerization Catalyst of thePresent Invention

At the time of obtaining an olefin polymerization catalyst by using anolefin polymerization catalyst component containing (A) a metallocenecompound as an essential component of the olefin polymerization catalystcomponent of the present invention, (B) a compound, as the sameessential component, capable of reacting with the metallocene compound(A) to produce a cationic metallocene compound, and (C) a microparticlesupport as a preferred component, the method for contacting respectivecomponents is not particularly limited and, for example, the followingmethods can be arbitrarily employed.

(I) A method of contacting the metallocene compound (A) with thecompound (B) capable of reacting with the metallocene compound (A) toproduce a cationic metallocene compound and thereafter, contacting themicroparticle support (C).

(II) A method of contacting the metallocene compound (A) with themicroparticle support (C) and thereafter, contacting the compound (B)capable of reacting with the metallocene compound (A) to produce acationic metallocene compound.

(III) A method of contacting the compound (B) capable of reacting withthe metallocene compound (A) to produce a cationic metallocene compoundwith the microparticle support (C) and thereafter, contacting themetallocene compound (A).

Among these contacting methods, the methods of (I) and (III) arepreferred, and the method of (I) is most preferred. In the contactingmethods above, the essential component (A-1b) and the essentialcomponent (A-2b), which are the metallocene compound (A), may be treatedafter mixing or may be separately treated, and, for example, a method ofusing the component (A-1 b) by the method of (I) among specific examplesabove and using the component (A-2b) by the method of (III) may be alsoemployed.

In all of these contacting methods, generally, a method of contactingrespective components with or without stirring in an inert atmosphere ofnitrogen, argon or the like in the presence of a liquid inerthydrocarbon, for example, an aromatic hydrocarbon (usually having acarbon number of 6 to 12) such as benzene, toluene, xylene andethylbenzene, or an aliphatic or alicyclic hydrocarbon (usually having acarbon number of 5 to 12) such as heptane, hexane, decane, dodecane andcyclohexane, is usually employed.

This contact is preferably performed usually at a temperature of −100 to200° C., preferably from −50 to 100° C., more preferably from 0 to 50°C., for 5 minutes to 50 hours, preferably from 30 minutes to 24 hours,more preferably from 30 minutes to 12 hours.

Also, at the time of containing the metallocene compound (A), thecompound (B) capable of reacting with the metallocene compound (A) toproduce a cationic metallocene compound, and the microparticle support(C), as described above, both an aromatic hydrocarbon solvent in which acertain component is soluble or sparingly soluble, and an aliphatic oralicyclic hydrocarbon solvent in which a certain component is insolubleor sparingly soluble, can be used.

In the case of stepwise performing the contact reaction of respectivecomponents with each other, the solvent and the like used in theprevious stage need not be removed but may be used directly for thesolvent in the contact reaction in the latter stage. Also, after theprevious-stage contact reaction using a soluble solvent, the desiredproduct may be collected as a solid matter by adding a liquid inerthydrocarbon (for example, an aliphatic hydrocarbon, an alicyclichydrocarbon or an aromatic hydrocarbon, such as pentane, hexane, decane,dodecane, cyclohexane, benzene and toluene) in which a certain componentis insoluble or sparingly soluble, or the desired product may be takenout as a solid matter by once removing a part or the whole of thesoluble solvent by means of drying or the like, and thereafter, thelatter-stage contact reaction of the desired product may be performedusing any of the above-described inert hydrocarbon solvents. In thepresent invention, the contact reaction of respective components may beperformed a plurality of times.

In the present invention, the ratio at which the metallocene compound(A), the compound (B) capable of reacting with the metallocene compound(A) to produce a cationic metallocene compound, and the microparticlesupport (C) are used is not particularly limited, but the followingranges are preferred.

The ratio between the component (A-1b) and the component (A-2b) that arethe metallocene compound (A) is set in an arbitrary range according tothe material properties required of the olefin-based polymer as a finalproduct but usually, letting the total of both components be 100, theratio is from 1:99 to 99.9:0.1, preferably from 5:95 to 99.5:0.5, morepreferably from 10:90 to 99.5:0.5, still more preferably from 20:80 to99.5:0.5, yet still more preferably from 40:60 to 99.2:0.8. If the ratioof the component (A-1b) is less than 1, the moldability of aolefin-based polymer as the product may not be enhanced due to lackingin production of a macromer and insufficient formation of a long-chainbranch, or since the component (A-2b) for producing a polymer having ahigher molecular weight becomes a main active species, polymerizationmust be performed under the condition having much hydrogen that is amolecular weight adjusting agent, namely, under the conditiondisadvantageous for production of a long-chain branch, as a result, themoldability is still not enhanced or a polymer produced from a smallamount of the component (A-1b) is more reduced in the molecular weight,making the product sticky, which is not preferred. If the ratio of thecomponent (A-1b) exceeds 99.9, it becomes difficult to sufficientlyincrease the molecular weight of the produced polymer, or the long-chainbranch does not grow to a high enough molecular weight,disadvantageously failing in enhancing the moldability. In thisconnection, selection of the molar ratio between the component (A-1b)and the component (A-2b) varies depending on whether the olefinpolymerization activities of both components greatly differ or are atthe same level, and therefore, needless to say, the molar ratio must beconsistently optimized according to the material properties of thetarget olefin-based polymer.

In the case of using an organoaluminum oxy compound as the compound (B)capable of reacting with the metallocene compound (A) to produce acationic metallocene compound, the atom ratio (Al/M) of aluminum of theorganoaluminum oxy compound to the transition metal (M) in themetallocene compound (A) is usually from 1 to 100,000, preferably from 5to 1,000, more preferably from 50 to 200. In the case of using a boranecompound or a borate compound, the atom ratio (B/M) of boron to thetransition metal (M) in the metallocene compound is preferably selectedin the range of usually from 0.01 to 100, preferably from 0.1 to 50,more preferably from 0.2 to 10.

Furthermore, in the case of using a mixture of an organoaluminum oxycompound and a borane or borate compound as the compound (B) forproducing a cationic metallocene compound, each compound in the mixtureis preferably used at the same ratio to the transition metal (M) asabove.

The amount of the microparticle support (C) used is preferably 1 g for0.0001 to 5 mmol, preferably for 0.001 to 0.5 mmol, more preferably for0.01 to 0.1 mmol, of the transition metal in the metallocene compound(A).

The metallocene compound (A), the compound (B) capable of reacting withthe metallocene compound (A) to produce a cationic metallocene compound,and the microparticle support (C) are contacted by any one of thecontacting methods (I) to (III) above and thereafter, the solvent isremoved, whereby the olefin polymerization catalyst can be obtained as asolid catalyst. The removal of the solvent is preferably performed underatmospheric pressure or reduced pressure at 0 to 200° C., preferably at20 to 150° C., for 1 minute to 50 hours, preferably for 10 minutes to 10hours.

Incidentally, the olefin polymerization catalyst can be also obtained bythe following method.

(IV) The metallocene compound (A) and the microparticle support (C) arecontacted and after removing the solvent, the obtained solid catalystcomponent is brought into contact with an organoaluminum oxy compound, aborane compound, a borate compound or a mixture thereof.

(V) An organoaluminum oxy compound, a borane compound, a borate compoundor a mixture thereof is brought into contact with the microparticlesupport (C) and after removing the solvent, the obtained solid catalystcomponent is brought into contact with the metallocene compound (A)under polymerization conditions.

Also in these contacting methods of (IV) and (V), the same conditions asabove can be used for the component ratio, the contacting conditions andthe solvent removing conditions.

The thus-obtained olefin polymerization catalyst may be used afterperforming preliminary polymerization of a monomer, if desired.

It is also preferred that the olefin polymerization catalyst componentor olefin polymerization catalyst of the present invention furthercontains a component (D): an organoaluminum compound. Examples of theorganoaluminum compound used here include an organoaluminum compounddescribed also in formula (11b), such as trimethylaluminum,triethylaluminum, triisobutylaluminum, diethylaluminum chloride andethylaluminum dichloride; an alkoxide having a carbon number of 1 to 18,preferably from 1 to 12, such as diethylaluminum ethoxide, ethylaluminumdiethoxide and dimethylaluminum ethoxide; an organoaluminum compoundhaving an oxygen-containing hydrocarbon group, such as alkenyloxy; theabove-described organoaluminum oxy compound; and a modifiedorganoaluminum compound having a branched alkyl group. Among these,trimethylaluminum, triethylaluminum, triisobutylaluminum,diethylaluminum chloride, ethylaluminum dichloride and diethylaluminumethoxide are preferred, triethylaluminum, triisobutylaluminum anddiethylaluminum chloride are more preferred, triethylaluminum andtriisobutylaluminum are still more preferred, and triethylaluminum isyet still more preferred.

IV-4. Use of Olefin Polymerization Catalyst of the Present Invention

The olefin polymerization catalyst of the present invention can be usedfor homopolymerization of an olefin or for copolymerization of an olefinand another olefin.

Here, the olefin includes an olefin having a carbon number of 2 to 30,preferably from 2 to 8, and is preferably ethylene or an α-olefin.Specific examples thereof include ethylene, propylene, 1-butene,1-hexene, 1-octene, and 4-methyl-1-pentene. Homopolymerization ofethylene or copolymerization of ethylene and the α-olefin above is morepreferred, and homopolymerization of ethylene, copolymerization ofethylene.propylene, copolymerization of ethylene.1-butene,copolymerization of ethylene.1-hexene, or copolymerization ofethylene.1-octene is still more preferred.

As the olefin, it is also possible to copolymerize three or more kindsof olefins.

The copolymerization may be any of alternating copolymerization, randomcopolymerization and block copolymerization. In the case ofcopolymerizing ethylene with another α-olefin, the amount of the anotherα-olefin may be arbitrarily selected in the range of 90 mol % or less ofall monomers but is generally 40 mol % or less, preferably 30 mol % orless, more preferably 10 mol % or less. Of course, a small amount of acomonomer other than ethylene and an α-olefin may be used, and in thiscase, the comonomer includes a compound having a polymerizable doublebond, for example, styrenes such as styrene, 4-methylstyrene and4-dimethylaminostyrene, dienes such as 1,4-butadiene, 1,5-hexadiene,1,4-hexadiene and 1,7-octadiene, a cyclic compound such as norbomene andcyclopentene, and oxygen-containing compounds such as hexenol, hexenoicacid and methyl octenoate.

In the present invention, the polymerization reaction may be performedpreferably by slurry polymerization or gas phase polymerization in thepresence of the above-described catalyst, preferably a supportedcatalyst.

In the case of slurry polymerization, ethylene or the like ispolymerized, while substantially blocking oxygen, water and the like, inthe presence or absence of an inert hydrocarbon solvent selected from analiphatic hydrocarbon such as isobutane, hexane and heptane, an aromatichydrocarbon such as benzene, toluene and xylene, and an alicyclichydrocarbon such as cyclohexane and methylcyclohexane. Needless to say,a liquid monomer such as liquid ethylene and liquid propylene can bealso used as the solvent.

In the case of gas phase polymerization, ethylene or the like ispolymerized in a reactor in which a gas flow of ethylene or a comonomeris introduced, distributed or circulated.

In the present invention, the polymerization is more preferably gasphase polymerization. The polymerization conditions usually employed aresuch that the temperature is from 0 to 250° C., preferably from 20 to110° C., more preferably from 60 to 100° C., the pressure is fromatmospheric pressure to 10 MPa, preferably from atmospheric pressure to4 MPa, more preferably from 0.5 to 2 MPa, and the polymerization time isfrom 5 minutes to 10 hours, preferably from 5 minutes to 5 hours.

The molecular weight of the produced polymer may be adjusted to acertain extent by changing the polymerization conditions such aspolymerization temperature and molar ratio of catalyst, but themolecular weight can be more effectively adjusted by adding hydrogen tothe polymerization reaction system.

Also, even when a component aiming at removing water, so-called ascavenger, is added to the reaction system, the polymerization can beperformed without causing any trouble.

Examples of the scavenger used here include the organoaluminum compounddescribed also in formula (11b) above, such as trimethylaluminum,triethylaluminum and triisobutylaluminum; the above-describedorganoaluminum oxy compound; a modified organoaluminum compound having abranched alkyl; an organozinc compound such as diethylzinc anddibutylzinc; an organomagnesium compound such as diethylmagnesium,dibutylmagnesium and ethylbutylmagnesium; and a Grignard compound suchas ethylmagnesium chloride and butylmagnesium chloride. Among these,triethylaluminum, triisobutylaluminum and ethylbutylmagnesium arepreferred, and triethylaluminum is more preferred.

The present invention can be applied without any trouble also for amultistage polymerization system consisting of two or more stages, inwhich polymerization conditions such as hydrogen concentration, monomeramount, polymerization pressure and polymerization temperature aredifferent from one another.

[V] Production Method of Ethylene-Base Polymer of the Present Invention

A fourth aspect of the present invention is to provide ametallocene-based polyolefin having a sufficient number of long-chainbranches having an appropriate length, preferably a metallocene-basedpolyethylene having a sufficient number of long-chain branches having anappropriate length. The fourth aspect of the present invention isdescribed below item by item.

V-1. Olefin Polymerization Catalyst

The production method of an olefin-based polymer of the presentinvention, preferably the production method of an ethylene-basedpolymer, is performed using an olefin polymerization catalyst containingthe following components (A) and (B) and, if desired, containing thecomponent (C).

Component (A): at least any one of the following catalyst components:

(A-i) an olefin polymerization catalyst component containing thecomponents (A-1b) and (A-2b) described in Item IV-1,

(A-ii) an olefin polymerization catalyst component containing thecomponent (Ac) described in Item IV-2, and

(A-iii) an olefin polymerization catalyst component containing ametallocene compound represented by the following formula (1d):

[in formula (1d), M^(1d) represents any one transition metal of Ti, Zrand Hf; each of X^(1d) and X^(2d) independently represents a hydrogenatom, a halogen atom, a hydrocarbon group having a carbon number of 1 to20, a hydrocarbon group containing an oxygen atom or a nitrogen atom andhaving a carbon number of 1 to 20, a hydrocarbon group-substituted aminogroup having a carbon number of 1 to 20, or an alkoxy group having acarbon number of 1 to 20; each of Q^(1d) and Q^(2d) independentlyrepresents a carbon atom, a silicon atom or a germanium atom; eachR^(1d) independently represents a hydrogen atom or a hydrocarbon grouphaving a carbon number of 1 to 10 and at least two members out of fourR^(1d) may combine to form a ring together with Q^(1d) and Q^(2d): m^(d)is 0 or 1 and when m^(d) is 0, Q^(1d) is bonded directly to theconjugated 5-membered ring including R^(2d) and R^(3d); each of R^(2d)and R^(3d) represents a hydrogen atom, a halogen atom, a hydrocarbongroup having a carbon number of 1 to 20, a silicon-containinghydrocarbon group containing from 1 to 6 silicons and having a carbonnumber of 1 to 18, a halogen-containing hydrocarbon group having acarbon number of 1 to 20, a hydrocarbon group containing an oxygen atomand having a carbon number of 1 to 20, or a hydrocarbongroup-substituted silyl group having a carbon number of 1 to 20,provided that at least one R^(2d) is not a hydrogen atom; R^(4d)represents a saturated or unsaturated divalent hydrocarbon group havinga carbon number of 4 or 5 for forming a condensed ring with the5-membered ring to which R^(4d) is bonded; R^(5d) is an atom or a groupbonded to a carbon atom of R^(4d) and each independently represents ahydrogen atom, a halogen atom, a hydrocarbon group having a carbonnumber of 1 to 20, a silicon-containing hydrocarbon group containingfrom 1 to 6 silicons and having a carbon number of 1 to 18, ahalogen-containing hydrocarbon group having a carbon number of 1 to 20,a hydrocarbon group containing an oxygen atom and having a carbon numberof 1 to 20, or a hydrocarbon group-substituted silyl group having acarbon number of 1 to 20; and n^(d) represents an integer of 0 to 10 andwhen n^(d) is 2 or more, at least two R^(5d) may form a ring togetherwith the carbon atoms to which R^(5d) are bonded],

Component (B): a compound capable of reacting with a metallocenecompound of the component (A) to produce a cationic metallocenecompound, and

Component (C): a microparticle support.

The olefin polymerization catalyst used in the production method of anethylene-based polymer, described as (A-iii) above, is characterized bycontaining a metallocene compound (Ad) represented by formula (1d) as anessential component.

In formula (1d). M^(1d) of the metallocene compound represents Ti, Zr orHf. M^(1d) of the metallocene compound preferably represents Zr or Hf,and M^(1d) of the metallocene compound more preferably represents Zr.

Each of X^(1d) and X^(2d) independently includes, for example, ahydrogen atom, a chlorine atom, a bromine atom, an iodine atom, a methylgroup, an ethyl group, an n-propyl group, an i-propyl group, an n-butylgroup, an i-butyl group, a tert-butyl group, an n-pentyl group, aneopentyl group, a cyclopentyl group, an n-hexyl group, a cyclohexylgroup, a phenyl group, a benzyl group, a methoxymethyl group, anethoxymethyl group, an n-propoxymethyl group, an i-propoxymethyl group,an n-butoxymethyl group, an i-butoxymethyl group, a tert-butoxymethylgroup, a methoxyethyl group, an ethoxyethyl group, an acetyl group, a1-oxopropyl group, a 1-oxo-n-butyl group, a 2-methyl-1-oxopropyl group,a 2,2-dimethyl-1-oxo-propyl group, a phenylacetyl group, adiphenylacetyl group, a benzoyl group, a 2-methoxyphenyl group, a3-methoxyphenyl group, a 4-methoxyphenyl group, a 2-furyl group, a2-tetrahydrofuryl group, a dimethylaminomethyl group, adiethylaminomethyl group, a di-i-propylaminomethyl group, abis(dimethylamino)methyl group, a bis(di-i-propylamino)methyl group, a(dimethylamino)(phenyl)methyl group, a methylimino group, an ethyliminogroup, a 1-(methylimino)ethyl group, a 1-(phenylimino)ethyl group, a1-[(phenylmethyl)imino]ethyl group, an ethoxy group, an n-propoxy group,an i-propoxy group, an n-butoxy group, an i-butoxy group, a tert-butoxygroup, a phenoxy group, a dimethylamino group, a diethylamino group, adi-n-propylamino group, a di-i-propylamino group, a di-n-butylaminogroup, a di-i-butylamino group, a di-tert-butylamino group, and adiphenylamino group.

Specific preferred examples of X^(1d) and X^(2d) include a chlorineatom, a bromine atom, a methyl group, an n-butyl group, an i-butylgroup, a methoxy group, an ethoxy group, an i-propoxy group, an n-butoxygroup, a phenoxy group, a dimethylamino group, and a di-i-propylaminogroup. Among these specific examples, a chlorine atom, a methyl groupand a dimethylamino group are more preferred.

Each of Q^(1d) and Q^(2d) independently represents a carbon atom, asilicon atom or a germanium atom and is preferably a carbon atom or asilicon atom, more preferably a silicon atom.

Each R^(1d) independently includes, for example, a hydrogen atom, amethyl group, an ethyl group, an n-propyl group, an i-propyl group, ann-butyl group, an i-butyl group, a tert-butyl group, an n-pentyl group,a neopentyl group, a cyclopentyl group, an n-hexyl group, a cyclohexylgroup, and a phenyl group. In the case where R^(1d) forms a ringtogether with Q^(1d) and Q^(2d), examples include a cyclobutylidenegroup, a cyclopentylidene group, a cyclohexylidene group, asilacyclobutyl group, a silacyclopentyl group, and a silacyclohexylgroup.

When Q^(1d) or/and Q^(2d) are a carbon atom, specific preferred examplesof R^(1d) include a hydrogen atom, a methyl group, an ethyl group, aphenyl group and a cyclobutylidene group, and when Q^(1d) or/and Q^(2d)are a silicon atom, specific preferred examples include a methyl group,an ethyl group, a phenyl group and a silacyclobutyl group.

Each of R^(2d) and R^(3d) includes, for example, a hydrogen atom, achlorine atom, a bromine atom, an iodine atom, a methyl group, an ethylgroup, an n-propyl group, an i-propyl group, an n-butyl group, ani-butyl group, a tert-butyl group, an n-pentyl group, a neopentyl group,a cyclopentyl group, an n-hexyl group, a cyclohexyl group, a phenylgroup, a benzyl group, a 2-methylphenyl group, a 3-methylphenyl group, a4-methylphenyl group, a 3,5-dimethylphenyl group, a 4-tert-butylphenylgroup, a 3,5-di-tert-butylphenyl group, a bis(trimethylsilyl)methylgroup, a bis(tert-butyldimethylsilyl)methyl group, a bromomethyl group,a chloromethyl group, a 2-chloroethyl group, a 2-bromoethyl group, a2-bromopropyl group, a 3-bromopropyl group, a 2-bromocyclopentyl group,a 2,3-dibromocyclopentyl group, a 2-bromo-3-iodocyclopentyl group, a2,3-dibromocyclohexyl group, a 2-chloro-3-iodocyclohexyl group, a2-chlorophenyl group, a 4-chlorophenyl group, a2,3,4,5,6-pentafluorophenyl group, a 4-trifluoromethylphenyl group, afuryl group, a tetrahydrofuryl group, a 2-methylfuryl group, atrimethylsilyl group, a tri-tert-butylsilyl group, adi-tert-butylmethylsilyl group, a tert-butyldimethylsilyl group, atriphenylsilyl group, a diphenylmethylsilyl group, and aphenyldimethylsilyl group.

Each of R^(2d) and R^(3d) is preferably a hydrocarbon group having acarbon number of 1 to 20, a silicon-containing hydrocarbon groupcontaining from 1 to 6 silicons and having a carbon number of 1 to 18, ahalogen-containing hydrocarbon group having a carbon number of 1 to 20,a hydrocarbon group containing an oxygen atom and having a carbon numberof 1 to 20, or a hydrocarbon group-substituted silyl group having acarbon number of 1 to 20, because the polymerization activity becomeshigh in particular. Furthermore, R^(2d) is preferably a hydrocarbongroup having a carbon number of 1 to 20, because the moldability of thepolyethylene is excellent in particular.

Specific preferred examples of R^(2d) and R^(3d) include a hydrogenatom, a methyl group, an ethyl group, an n-propyl group, an i-propylgroup, an n-butyl group, a tert-butyl group, an n-pentyl group, ann-hexyl group, a cyclohexyl group, a phenyl group, a 2-methylfurylgroup, and a trimethylsilyl group. Among these specific examples, ahydrogen atom, a methyl group, an n-butyl group, a tert-butyl group, aphenyl group and a trimethylsilyl group are more preferred, and ahydrogen atom, a methyl group, a tert-butyl group, a phenyl group and atrimethylsilyl group are still more preferred.

Specific examples of the condensed cyclopentadienyl structure formed byR^(4d) and a cyclopentadienyl moiety to which R^(4d) is bonded, includethe following partial structures (I) to (VI).

Among these specific examples, (I), (III) and (VI) are preferred. Also,R^(5d) may be substituted on these partial structures (I) to (VI).

The substituent R^(5d) includes, in addition to a hydrogen atom, forexample, a chlorine atom, a bromine atom, an iodine atom, a methylgroup, an ethyl group, an n-propyl group, an i-propyl group, an n-butylgroup, an i-butyl group, a tert-butyl group, an n-pentyl group, aneopentyl group, a cyclopentyl group, an n-hexyl group, a cyclohexylgroup, a phenyl group, a benzyl group, a 2-methylphenyl group, a3-methylphenyl group, a 4-methylphenyl group, a 4-tert-butylphenylgroup, a 3,5-dimethylphenyl group, a 3,5-di-tert-butylphenyl group, anaphthyl group, an anthracenyl group, a bis(trimethylsilyl)methyl group,a bis(tert-butyldimethylsilyl)methyl group, a bromomethyl group, achloromethyl group, a 2-chloroethyl group, a 2-bromoethyl group, a2-bromopropyl group, a 3-bromopropyl group, a 2-bromocyclopentyl group,a 2,3-dibromocyclopentyl group, a 2-bromo-3-iodocyclopentyl group, a2,3-dibromocyclohexyl group, a 2-chloro-3-iodocyclohexyl group, a2-chlorophenyl group, a 4-chlorophenyl group, a2,3,4,5,6-pentafluorophenyl group, a 2,6-dichloro-4-trimethylsilylphenylgroup, a trimethylsilyl group, a tri-tert-butylsilyl group, adi-tert-butylmethylsilyl group, a tert-butyldimethylsilyl group, atriphenylsilyl group, a diphenylmethylsilyl group, and aphenyldimethylsilyl group.

In the case where two or more R^(5d) form a ring together with thecarbon atoms to which R^(5d) are bonded, examples include abenz[e]indenyl group, a benz[f]indenyl group, a 6,7-dihydroindacenylgroup, a 5,5,7,7-tetramethyl-6,7-dihydroindacenyl group, a5,6,7,8-tetrahydro-benz[f]indenyl group, and a5,6,7,8-tetrahydro-5,5,8,8-tetramethyl-benz[f]indenyl group.

Specific preferred examples of R^(5d) include a methyl group, an ethylgroup, an n-propyl group, an i-propyl group, an n-butyl group, atert-butyl group, an n-pentyl group, an n-hexyl group, a cyclohexylgroup, a phenyl group, a naphthyl group, and a trimethylsilyl group.

In formula (1d), m^(d) is 0 or 1 and when m^(d) is 0, Q^(1d) is bondeddirectly to the conjugated 5-membered ring including R^(3d).Furthermore, n^(d) represents an integer of 0 to 10 and when n^(d) is 2or more, at least two R^(5d) may form a ring together with the carbonatoms to which R^(5d) are bonded.

As the olefin polymerization catalyst according to the presentinvention, the metallocene compound of the essential component (Ad) ispreferably a compound represented by the following formula (2d):

In the metallocene compound represented by formula (2d), for M^(1d),X^(1d), X^(2d), Q^(1d), R^(1d), R^(2d), R^(3d), R^(4d) and R^(5d), thesame structures as the atoms and groups described in the metallocenecompound represented by formula (1d) may be selected.

As the olefin polymerization catalyst according to the presentinvention, the metallocene compound of the essential component (Ad) ismore preferably a compound represented by the following formula (3d):

In the metallocene compound represented by formula (3d), for M^(1d),X^(1d), X^(2d), Q^(1d), R^(1d) and R^(2d), the same structures as theatoms and groups described in the metallocene compound represented byformula (1d) may be selected.

Specific examples of the metallocene compound as the essential component(Ad) of the olefin polymerization catalyst for use in the productionmethod of an ethylene-based polymer of the present invention are shownby formula (4d) and in Tables d-1 to d-4 below, but the presentinvention is not limited thereto. In Tables d-1 to d-4. TMS stands fortrimethylsilyl, Ind stands for an indenyl group, and Cp stands for acyclopentadienyl group.

Incidentally, the number indicating the position of each substituent onthe cyclopentadienyl ring and indenyl ring of metallocene compoundsrecited as specific examples is as shown in the following formula (5d).

TABLE d-1 Ind-3-R^(3d)- No. M^(1d) X^(1d), X^(2d) R^(1d) ₂Q^(1d)Cp-2,3,4,5-R^(2d) ₄ 4,5,6,7-R^(5d) ₄  1d Zr Cl Me₂Si 4-tBu-Cp Ind  2d ZrCl Me₂Si 3-tBu-Cp Ind  3d Zr Cl Me₂Si 4-TMS-Cp Ind  4d Zr Cl Me₂Si3-TMSCp Ind  5d Zr Cl Me₂Si 4-Me-Cp Ind  6d Zr Cl Me₂Si 3-Me-Cp Ind  7dZr Cl Me₂Si 4-Et-Cp Ind  8d Zr Cl Me₂Si 3-Et-Cp Ind  9d Zr Cl Me₂Si4-nPr-Cp Ind 10d Zr Cl Me₂Si 3-nPr-Cp Ind 11d Zr Cl Me₂Si 4-iPr-Cp Ind12d Zr Cl Me₂Si 3-iPr-Cp Ind 13d Zr Cl Me₂Si 4-nBu-Cp Ind 14d Zr ClMe₂Si 3-nBu-Cp Ind 15d Zr Cl Me₂Si 4-iBu-Cp Ind 16d Zr Cl Me₂Si 3-iBu-CpInd 17d Zr Cl Me₂Si 4-Ph-Cp Ind 18d Zr Cl Me₂Si 3-Ph-Cp Ind 19d Zr ClMe₂Si 4-Et₃Si-Cp Ind 20d Zr Cl Me₂Si 3-Et₃Si-Cp Ind 21d Zr Cl Me₂Si4-nPr₃Si-Cp Ind 22d Zr Cl Me₂Si 3-nPr₃Si-Cp Ind 23d Zr Cl Me₂Si4-nBu₃Si-Cp Ind 24d Zr Cl Me₂Si 3-nBu₃Si-Cp Ind 25d Zr Cl Me₂Si4-iBu₃Si-Cp Ind 26d Zr Cl Me₂Si 3-iBu₃Si-Cp Ind 27d Zr Cl Me₂Si4-tri-n-pentylsilyl-Cp Ind 28d Zr Cl Me₂Si 3-tri-n-pentylsilyl-Cp Ind29d Zr Cl Me₂Si 4-tri-n-hexylsilyl-Cp Ind 30d Zr Cl Me₂Si3-tri-n-hexylsilyl-Cp Ind 31d Zr Cl Me₂Si 4-trivinylsilyl-Cp Ind 32d ZrCl Me₂Si 3-trivinylsilyl-Cp Ind 33d Zr Cl Me₂Si 4-Ph₃Si-Cp Ind 34d Zr ClMe₂Si 3-Ph₃Si-Cp Ind

TABLE d-2 (continued) Ind-3-R^(3d)- X^(1d), 4,5, No. M^(1d) X^(2d)R^(1d) ₂Q^(1d) Cp-2,3,4,5-R^(2d) ₄ 6,7-R^(5d) ₄ 35d Zr Cl Me₂Si4-tribenzylsilyl-Cp Ind 36d Zr Cl Me₂Si 3-tribenzylsilyl-Cp Ind 37d ZrCl Me₂Si 4-tBuMe₂Si-Cp Ind 38d Zr Cl Me₂Si 3-tBuMe₂Si-Cp Ind 39d Zr ClMe₂Si 2,4-Me₂-Cp Ind 40d Zr Cl Me₂Si 3,5-Me₂-Cp Ind 41d Zr Cl Me₂Si2,4,5-Me₃-Cp Ind 42d Zr Cl Me₂Si 2,3,5-Me₃-Cp Ind 43d Zr Cl Me₂Si2,3,4,5-Me₄-Cp Ind 44d Zr Cl Me₂Si 2-Me-4-Ph-Cp Ind 45d Zr Cl Me₂Si3-Ph-5-Me-Cp Ind 46d Zr Me Me₂Si 4-tBu-Cp Ind 47d Zr Me Me₂Si 3-tBu-CpInd 48d Zr Me Me₂Si 4-TMS-Cp Ind 49d Zr Me Me₂Si 3-TMS-Cp Ind 50d Zr MeMe₂Si 4-Me-Cp Ind 51d Zr Me Me₂Si 3-Me-Cp Ind 52d Zr Ph Me₂Si 4-tBu-CpInd 53d Zr Ph Me₂Si 3-tBu-Cp Ind 54d Zr Ph Me₂Si 4-TMS-Cp Ind 55d Zr PhMe₂Si 3-TMSCp Ind 56d Zr NMe₂ Me₂Si 4-tBu-Cp Ind 57d Zr NMe₂ Me₂Si3-tBu-Cp Ind 58d Zr NMe₂ Me₂Si 4-TMS-Cp Ind 59d Zr NMe₂ Me₂Si 3-TMSCpInd 60d Zr Cl Et₂Si 4-tBu-Cp Ind 61d Zr Cl Et₂Si 3-tBu-Cp Ind 62d Zr ClEt₂Si 4-TMS-Cp Ind 63d Zr Cl Et₂Si 3-TMSCp Ind 64d Zr Cl Et₂Si 4-Ph-CpInd 65d Zr Cl Et₂Si 3-Ph-Cp Ind 66d Zr Cl Ph₂Si 4-tBu-Cp Ind 67d Zr ClPh₂Si 3-tBu-Cp Ind 68d Zr Cl Ph₂Si 4-TMS-Cp Ind 69d Zr Cl Ph₂Si 3-TMSCpInd 70d Zr Cl Ph₂Si 4-Ph-Cp Ind 71d Zr Cl Ph₂Si 3-Ph-Cp Ind 72d Zr Clsilacyclobutyl 4-tBu-Cp Ind 73d Zr Cl silacyclobutyl 3-tBu-Cp Ind 74d ZrCl silacyclobutyl 4-TMS-Cp Ind 75d Zr Cl silacyclobutyl 3-TMSCp Ind

TABLE d-3 (continued) Cp-2, Ind-3-R^(3d)- No. M^(1d) X^(1d), X^(2d)R^(1d) ₂Q^(1d) 3,4,5-R^(2d) ₄ 4,5,6,7-R^(5d) ₄ 76d Zr Cl silacyclobutyl4-Ph-Cp Ind 77d Zr Cl silacyclobutyl 3-Ph-Cp Ind 78d Zr Cl H₂C 4-tBu-CpInd 79d Zr Cl H₂C 3-tBu-Cp Ind 80d Zr Cl H₂C 4-TMS-Cp Ind 81d Zr Cl H₂C3-TMSCp Ind 82d Zr Cl H₂C 4-Ph-Cp Ind 83d Zr Cl H₂C 3-Ph-Cp Ind 84d ZrCl Me₂C 4-tBu-Cp Ind 85d Zr Cl Me₂C 3-tBu-Cp Ind 86d Zr Cl Me₂C 4-TMS-CpInd 87d Zr Cl Me₂C 3-TMSCp Ind 88d Zr Cl Me₂C 4-Ph-Cp Ind 89d Zr Cl Me₂C3-Ph-Cp Ind 90d Zr Cl Ph₂C 4-tBu-Cp Ind 91d Zr Cl Ph₂C 3-tBu-Cp Ind 92dZr Cl Ph₂C 4-TMS-Cp Ind 93d Zr Cl Ph₂C 3-TMSCp Ind 94d Zr Cl Ph₂C4-Ph-Cp Ind 95d Zr Cl Ph₂C 3-Ph-Cp Ind 96d Zr Cl cyclobutylidene4-tBu-Cp Ind 97d Zr Cl cyclobutylidene 3-tBu-Cp Ind 98d Zr Clcyclobutylidene 4-TMS-Cp Ind 99d Zr Cl cyclobutylidene 3-TMSCp Ind 100d Zr Cl cyclobutylidene 4-Ph-Cp Ind 101d  Zr Cl cyclobutylidene 3-Ph-CpInd 102d  Zr Cl Et 4-tBu-Cp Ind 103d  Zr Cl Et 3-tBu-Cp Ind 104d  Zr ClEt 4-TMS-Cp Ind 105d  Zr Cl Et 3-TMSCp Ind 106d  Zr Cl Et 4-Ph-Cp Ind107d  Zr Cl Et 3-Ph-Cp Ind 108d  Zr Cl Me₂Ge 4-tBu-Cp Ind 109d  Zr ClMe₂Ge 3-tBu-Cp Ind 110d  Zr Cl Me₂Ge 4-TMS-Cp Ind 111d  Zr Cl Me₂Ge3-TMSCp Ind 112d  Zr Cl Me₂Ge 4-Ph-Cp Ind 113d  Zr Cl Me₂Ge 3-Ph-Cp Ind114d  Zr Cl Me₂Si 4-tBu-Cp 3-Me-Ind 115d  Zr Cl Me₂Si 3-tBu-Cp 3-Me-Ind

TABLE d-4 (continued) Ind-3-R^(3d)- No. M^(1d) X^(1d), X^(2d) R^(1d)₂Q^(1d) Cp-2,3,4,5-R^(2d) ₄ 4,5,6,7-R^(5d) ₄ 116d Zr Cl Me₂Si 4-TMS-Cp3-Me-Ind 117d Zr Cl Me₂Si 3-TMSCp 3-Me-Ind 118d Zr Cl Me₂Si 4-tBu-Cp3-iPr-Ind 119d Zr Cl Me₂Si 3-tBu-Cp 3-iPr-Ind 120d Zr Cl Me₂Si 4-TMS-Cp3-iPr-Ind 121d Zr Cl Me₂Si 3-TMSCp 3-iPr-Ind 122d Zr Cl Me₂Si 4-tBu-Cp3-tBu-Ind 123d Zr Cl Me₂Si 3-tBu-Cp 3-tBu-Ind 124d Zr Cl Me₂Si 4-TMS-Cp3-tBu-Ind 125d Zr Cl Me₂Si 3-TMSCp 3-tBu-Ind 126d Zr Cl Me₂Si 4-tBu-Cp3-TMS-Ind 127d Zr Cl Me₂Si 3-tBu-Cp 3-TMS-Ind 128d Zr Cl Me₂Si 4-TMS-Cp3-TMS-Ind 129d Zr Cl Me₂Si 3-TMSCp 3-TMS-Ind 130d Zr Cl Me₂Si 4-tBu-Cp3-Ph-Ind 131d Zr Cl Me₂Si 3-tBu-Cp 3-Ph-Ind 132d Zr Cl Me₂Si 4-TMS-Cp3-Ph-Ind 133d Zr Cl Me₂Si 3-TMSCp 3-Ph-Ind 134d Zr Cl Me₂C 4-tBu-Cp3-Me-Ind 135d Zr Cl Me₂C 3-tBu-Cp 3-Me-Ind 136d Zr Cl Me₂C 4-TMS-Cp3-Me-Ind 137d Zr Cl Me₂C 3-TMSCp 3-Me-Ind 138d Zr Cl Me₂C 4-tBu-Cp3-iPr-Ind 139d Zr Cl Me₂C 3-tBu-Cp 3-iPr-Ind 140d Zr Cl Me₂C 4-TMS-Cp3-iPr-Ind 141d Zr Cl Me₂C 3-TMSCp 3-iPr-Ind 142d Zr Cl Me₂C 4-tBu-Cp3-tBu-Ind 143d Zr Cl Me₂C 3-tBu-Cp 3-tBu-Ind 144d Zr Cl Me₂C 4-TMS-Cp3-tBu-Ind 145d Zr Cl Me₂C 3-TMSCp 3-tBu-Ind 146d Zr Cl Me₂C 4-tBu-Cp3-TMS-Ind 147d Zr Cl Me₂C 3-tBu-Cp 3-TMS-Ind 148d Zr Cl Me₂C 4-TMS-Cp3-TMS-Ind 149d Zr Cl Me₂C 3-TMSCp 3-TMS-Ind 150d Zr Cl Me₂C 4-tBu-Cp3-Ph-Ind 151d Zr Cl Me₂C 3-tBu-Cp 3-Ph-Ind 152d Zr Cl Me₂C 4-TMS-Cp3-Ph-Ind 153d Zr Cl Me₂C 3-TMSCp 3-Ph-Ind

The metallocene compound also includes, for example, compounds wherezirconium of the compounds above is replaced by titanium or hafnium.

Furthermore, in using these metallocene compounds as the essentialcomponent (Ad), two or more thereof may be also used.

Among specific compounds exemplified above, preferred metallocenecompounds as the essential component (Ad) are described below. Thecompounds include, for example, 1d-51d, 72d-77d, 84d-89d, 96d-101d,114d-129d, and 134d-149d in Tables d-1 to d-4.

Preferred metallocene compounds also include, for example, compoundswhere zirconium of the compounds above is replaced by titanium orhafnium.

Among specific compounds exemplified above, more preferred metallocenecompounds as the essential component (Ad) are described below. Thecompounds include, for example, 1d-6d, 17d, 18d, 46d-49d, 115d, 1174,118d, 121d, 123d, 125d, 127d, 129d, 135d, 137d, 139d, 141d, 143d, 145d,147d and 149d in Tables d-1 to d-4.

Preferred metallocene compounds also include, for example, compoundswhere zirconium of the compounds above is replaced by titanium orhafnium.

Furthermore, among specific compounds exemplified above, in terms ofhigh polymerization activity, still more preferred metallocene compoundsas the essential component (Ad) are described below. The compoundsinclude, for example, 1d-51, 114d-129d, and 134d to 149d in Tables d-1to d-4.

In addition, among specific compounds exemplified above, in terms ofexcellent mobility, still more preferred metallocene compounds as theessential component (Ad) are described below. The compounds include, forexample, 1d-6d, 17d, 18d, 46d-49d, 72d-77d, 84d-89d, 96d-101d, 115d,117d, 119d, 121d, 123d, 125d, 127d, 129d, 135d, 137d, 139d, 141d, 143d,145d, 147d and 149d in Tables d-1 to d-4.

Synthesis examples for the metallocene compound as the essentialcomponent (Ad) according to the present invention are described below,but the present invention is not limited to these synthesis methods inparticular.

For example, there are a method where an indene compound is lithioated,then reacted with a dichlorosilane compound and subsequently reactedwith a lithium salt of cyclopentadiene having a substituent to obtain aligand and the obtained ligand is reacted with atetrakis(alkylamido)zirconium and then with trimethylsilyl chloride, anda method where the obtained ligand is lithioated and subsequentlyreacted with zirconium tetrachloride.

V-2. Physical Properties (Characteristics) of Olefin-Based Polymer andEthylene-Based Polymer

By the polymerization method of the present invention, an olefin-basedpolymer or ethylene-based polymer described below is obtained. Here,physical properties of an ethylene-based polymer are mainly described.In the present invention, an ethylene-based polymer indicates anethylene homopolymer or an ethylene.α-olefin copolymer produced by theabove-described copolymerization.

The ethylene-based polymer produced by the production method of anethylene-based polymer of the present invention satisfies at least thecondition (B-4′) out of the conditions defined in the paragraph ofEthylene-Based Polymer of Item [III]. That is, λmax(2.0) of theethylene-based polymer is from 1.2 to 30.0, preferably from 1.5 to 20.0,more preferably from 2.0 to 10.0, still more preferably from 2.4 to 6.0,yet still more preferably from 3.0 to 5.0. The description of λmax(2.0)that must be satisfied by the ethylene-based polymer is as describedabove in the paragraph of condition (A-4) or condition (B-4) and isomitted here.

The ethylene-based polymer produced in the present invention is improvedin the melting properties as compared with normal ethylene-basedpolymers and is prominently characterized by having excellentmoldability.

In general, a polyethylene is processed into an industrial product by ashaping method involving a molten state, such film molding, blow moldingand foam molding, and at this time, it is well known that theelongational flow characteristics greatly affect the ease of molding.

That is, a polyethylene having a narrow molecular weight distributionand having no long-chain branch exhibits bad moldability because of itslow melt strength, whereas a polyethylene having an ultrahigh molecularweight component or a long-chain branch component has a property ofundergoing strain hardening during melt elongation, that is, abruptlyrising in the elongational viscosity on the high strain side, and apolyethylene exhibiting this property outstandingly is said to beexcellent in the moldability.

As the method for quantitatively expressing this elongational viscosityproperty, there is a method where the ratio between the elongationalviscosity before strain hardening and the elongational viscosity afterstrain hardening is calculated as a degree of strain hardening (max),and this is useful as an indicator of non-linearity of the elongationalviscosity. When the λmax value is high, this has an effect of preventinguneven wall thickness or blown rupture of a product in the film moldingor blow molding, enabling high-speed molding, or making it possible toraise the percentage of closed pores at the foam molding and providesfor merits such as increase of strength of a molded article, enhancementof design property, reduction in weight, improvement of molding cycle,and elevation of heat insulating property.

The ethylene-based polymer produced in the present invention has quitecharacteristic elongational viscosity property, molecular weightdistribution and intrinsic viscosity property based on itscharacteristic long-chain branched structure and furthermore, theethylene-based polymer produced by the production method of anethylene-based polymer of the present invention, which satisfies, inaddition to the condition (B-4′), preferably at least any one or more,more preferably two or more, still more preferably three or more, yetstill more preferably five or more, and most preferably all, of theabove-described conditions (B-1′), (B-2″), (B-3). (B-5), (B-7), (B-8)and (B-9), is improved particularly in the melt properties and providedwith excellent moldability in comparison to normal ethylene-basedpolymers and at the same time, is excellent also in the mechanicalproperties such as stiffness, impact strength and transparency.

EXAMPLES

The present invention is described in greater detail below by referringto Examples and Comparative Examples to demonstrate the excellence ofthe present invention and the advantage in the configuration of thepresent invention, but the present invention is not limited to theseExamples.

Incidentally, the measurement methods used in Examples and ComparativeExamples are as follows. In the following, all of the catalystsynthesizing process and the polymerization process were performed in apurified nitrogen atmosphere, and the solvent employed was dehydratedand purified using molecular sieve 4A and then used.

[Method for Measuring Degree of Strain Hardening of Ethylene-BasedPolymer]

The degree of strain hardening (λmax) of elongational viscosity wasmeasured using a Rheometer by the method included in the description ofthe present invention. Incidentally, in advance of preparation of a testspecimen, the dissolution.reprecipitation treatment of the polymer wasperformed according to the following procedure.

Into a 500 ml-volume two-neck flask with a cooling tube, 300 ml ofxylene was introduced and after performing nitrogen bubbling at roomtemperature for 30 minutes, 6.0 g of the polymer and 1.0 g of2,6-di-tert-butylhydroxytoluene (BTH) were introduced thereinto. In anitrogen atmosphere, the contents were stirred at 125° C. for 30 minutesto completely dissolve the polymer in xylene, and the xylene solutionhaving dissolved therein the polymer was poured in 2.5 L of ethanol toprecipitate the polymer. The polymer was collected by filtration anddried in a vacuum drier at 80° C.

[Measurement of Number of Terminal Double Bonds]

As for the quantitative determination of the terminal double bond, apress film was produced, and after measuring the infrared absorptionspectrum (IR) by using an apparatus, FTIR-8300, manufactured by ShimadzuCorporation, the number of terminal double bonds was calculatedaccording to the following formula from the peak absorbance at 910 cm⁻¹.

Number of terminal double bonds (bonds/1000 carbons)=1.14×ΔA/d/t

wherein ΔA is the peak absorbance at 910 cm⁻¹.

[Measurement of Amount of Soluble Matters]

The sample was dissolved in orthodichlorobenzene (containing 0.5 mg/mLBHT) at 140° C. to prepare a solution, and the solution was introducedinto a TREF column at 140° C., then cooled to 100° C. at a temperaturedrop rate of 8° C./min, further cooled to −15° C. at a temperature droprate of 4° C./min and held for 60 minutes. Thereafter,orthodichlorobenzene (containing 0.5 mg/mL BHT) as a solvent was flowedthrough the column at a flow velocity of 1 mL/min to elute componentsdissolved in the orthodichlorobenzene at −15° C. in the TREF column for10 minutes, and then the column temperature was raised linearly to 140°C. at a temperature rise rate of 100° C./hr to obtain an elution curve.

Apparatus: (TREF Part)

TREF Column: Stainless steel-made column of 4.3 mmφ×150 mm

Column packing material: Surface-deactivated glass bead of 100 μm

Heating system: Aluminum heating block

Cooling system: Peltier element (cooling of Peltier element was watercooling)

Temperature distribution: ±0.5° C.

Temperature regulator: programmable digital controller, KP 1000,manufactured by Chino Corporation

(Valve Part)

Heating system: Air bath oven

Temperature at measurement: 140° C.

Temperature distribution: ±1° C.

Valve: Six-way valve, four-way valve

(Sample Injection Part)

Injection system: Loop injection system

Injection amount: Loop size, 0.1 ml

Injection port heating system: Aluminum heating block

Temperature at measurement: 140° C.

(Detector Part)

Detector: Wavelength-fixed infrared detector, MIRAN 1A, manufactured byFOXBORO

Detection wavelength: 3.42 μm

High-temperature flow cell: Micro-flow cell for LC-IR, optical pathlength: 1.5 mm, window shape: oval of 2φ×4 mm, synthetic sapphireaperture plate

Temperature at measurement: 140° C.

(Pump Part)

Liquid delivery pump: SSC-3461 pump, manufactured by Senshu Kagaku

Measurement Conditions:

Solvent: o-Dichlorobenzene (containing 0.5 mg/mL of BHT)

Sample concentration: 5 mg/mL

Sample injection amount: 0.1 mL

Solvent flow velocity: 1 mL/min

[Evaluation Method of Film] (1) Tensile Modulus

The tensile modulus at a deformation of 1% in the film processingdirection (MD direction) and the film width direction (TD direction) wasmeasured in accordance with JIS K7127-1999.

(2) Film Impact

A film-shaped test specimen was fixed on a holder having a diameter of50 mm and struck with a perforator having a specified tip diameter (ahemispherical type of 25.4 mmφ), and the energy (J/mm) required forperforation into fracture was measured. A higher value indicates thatthe impact strength is excellent.

A tester having a 900 arcuate arm capable of attaching a perforator tothe distal end was used in accordance with JS P8134.

(3) Transparency (Haze)

The transparency was measured in accordance with JIS K7105-1981. Asmaller value indicates that the transparency is excellent.

(4) Tear Strength (Elmendorf Tearing Method)

The tear strength (N/mm) in the film processing direction (MD direction)and the film width direction (TD direction) was measured in accordancewith JIS K7128-1991.

[Molding Conditions of Inflation Film and Evaluation Method ofMoldability]

At the time of molding a film of 30 μm, an inflation film was moldedunder the following molding conditions by using the following inflationfilm forming machine (molding apparatus) with an extruder of 30 mmφ, andevaluated.

Apparatus: Inflation molding apparatus

Screw diameter of extruder: 30 mmφ

Die diameter: 25 mmφ

Extrusion amount: 10 kg/hr

Lip gap of die: 2.0 mm

Taking-up speed: 6.0 m/min

Blow-up ratio: 2.0

Molding resin temperature: from 170 to 190° C. (shown in Examples)

Film thickness: 30 μm

Cooling ring: Single-slit air ring

At the time of molding a film of 50 μm, an inflation film was moldedunder the following molding conditions by using the following inflationfilm forming machine (molding apparatus) with an extruder of 50 mmφ0,and evaluated.

Apparatus: Inflation molding apparatus

Screw diameter of extruder: 50 mmφ

Die diameter: 75 mmφ

Extrusion amount: 20 kg/hr

Lip gap of die: 3.0 mm

Taking-up speed: 15 m/min

Blow-up ratio: 2.0

Molding resin temperature: from 170 to 190° C.

Film thickness: 50 μm

Cooling ring: Two-stage air-cooling ring

Example 1a(a) (1) Production of Ethylene-Based Polymer (A-1)[Preparation of Metallocene Catalyst A-1]

In a catalyst preparation apparatus equipped with an electromagneticinduction stirrer, under a nitrogen flow, 1,000 ml of purified toluene,22 g of tetraethoxyzirconium (Zr(OEt)₄), 75 g of indene and 88 g ofmethylbutylcyclopentadiene were added and while keeping the system at90° C., 100 g of tripropylaluminum was added dropwise over 100 minutesand then reacted at the same temperature for 2 hours. The reactionproduct was cooled to 40° C. and thereafter, 3,200 ml of a toluenesolution of methylalumoxane (concentration: 2.5 mmol/ml) was added.After stirring for 2 hours, 2,000 g of silica (#952, produced by Grace,surface area: 300 m²/g) previously subjected to a calcining treatment at450° C. for 5 hours was added and stirred at room temperature for 1hour. Thereafter, nitrogen blow at 40° C. and reduced-pressure dryingwere performed to obtain Solid Catalyst A-1 having good flowability.

[Production of Ethylene.1-Hexene Copolymer]

In a continuous gas-phase polymerization apparatus (inner volume: 100 L,diameter of fluidized bed: 10 cm, seed polymer of fluidized bed(dispersant): 1.5 kg) set such that the molar ratio of 1-hexene/ethyleneis 0.018, the molar ratio of hydrogen/ethylene is 2.9×10⁻⁴, the nitrogenconcentration is 30 mol %, the total pressure is 0.8 MPa and thetemperature is 80° C., a hexane solution (0.03 mmol/ml) oftriethylaluminum was fed at 7 ml/h and while keeping the gas compositionand the temperature constant, polymerization was performed byintermittently feeding Solid Catalyst A-1 to achieve a production yieldof about 320 g per hour. The activity was 420 g/(g of catalyst·MPa·h).When physical properties of the obtained Ethylene-Based Polymer (A-1)were measured, MFR was 2.0 g/10 min and the density was 0.918 g/cm³.

(2) Production of Ethylene-Based Polymer (B-1) [Preparation ofMetallocene Catalyst B-1]

Dimethylsilylene(cyclopentadienyl)(3-methylindenyl)zirconium dichloridewas synthesized using cyclopentadienyl-(3-methylindenyl)dimethylsilaneaccording to the procedure described in Macromolecules 1995, 28,3771-3778.

In a nitrogen atmosphere, 5 g of silica calcined at 600° C. for 5 hourswas put in a 200-ml two-neck flask and dried at reduced pressure with avacuum pump for 1 hour while heating the flask in an oil bath at 150° C.In a nitrogen atmosphere, 51.8 mg ofdimethylsilylene(cyclopentadienyl)(3-methylindenyl)zirconium dichloridesynthesized above was put in a separately prepared 100-ml two-neck flaskand dissolved in 13.4 ml of dehydrated toluene, and thereafter, 8.6 mlof a 20% methylaluminoxane/toluene solution produced by Albemarle wasfurther added at room temperature and stirred for 30 minutes. Whileheating the 200-ml two-neck flask containing vacuum-dried silica in anoil bath at 40° C. and stirring the contents, the entire amount of thetoluene solution above containing a reaction product of the complex andmethylaluminoxane was added and stirred at 40° C. for 1 hour. Whileheating the system at 40° C., the toluene solvent was removed bydistillation under reduced pressure to obtain Solid Catalyst B-1.

[Production of Ethylene.1-Hexene Copolymer]

Continuous gas-phase copolymerization of ethylene.1-hexene was performedusing Solid Catalyst B-1. That is, in a continuous gas-phasepolymerization apparatus (inner volume: 100 L, diameter of fluidizedbed: 10 cm, seed polymer of fluidized bed (dispersant): 1.8 kg) set suchthat the temperature is 75° C., the molar ratio of hexene/ethylene is0.012, the molar ratio of hydrogen/ethylene is 1.5×10⁻³, the nitrogenconcentration is 24 mol % and the total pressure is 0.8 MPa,polymerization was performed by keeping the gas composition and thetemperature constant while intermittently feeding the solid catalyst ata rate of 0.38 g/hour. Also, in order to maintain the cleanliness in thesystem, 0.03 mol/L of a triethylahuninum (TEA) solution diluted withhexane was fed at 7 ml/hr to a gas circulating line. As a result, theaverage production rate of the product polyethylene became 420 g/hour.After producing a polyethylene in a cumulative amount of 5 kg or more,the MFR and density of the obtained Ethylene-Based Polymer (B-1) were0.8 g/10 min and 0.914 g/cm³, respectively.

(3) Production of Polyethylene-Based Resin Composition 1a

A polyethylene resin at a mixing ratio of 95 wt % of Ethylene-BasedPolymer (A-1) and 5 wt % of Ethylene-Based Polymer (B-1) was mixed andhomogenized by a mixer.

The obtained mixture was melt-kneaded by a twin-screw extruder, and theextrudate was solidified and granulated. With respect to the finallyobtained Granular Polyethylene Resin Composition 1a, film moldabilityand film physical properties were evaluated by the above-describedmethod of molding a 50μ film. The results obtained are shown in Table1a-1 and Table 1a-2.

Example 1a(b)

Production of Polyethylene-Based Resin Composition 1b and film moldingwere performed in the same manner as in (1) to (3) of Example 1a(a)except that the mixing ratio of ethylene-based polymers was changed to90 wt % of Ethylene-Based Polymer (A-1) and 10 wt % of Ethylene-BasedPolymer (B-1). The results obtained are shown in Table 1a-1 and Table1a-2.

Example 1a(c)

Production of Polyethylene-Based Resin Composition 1c and film moldingwere performed in the same manner as in (1) to (3) of Example 1a(a)except that the mixing ratio of ethylene-based polymers was changed to80 wt % of Ethylene-Based Polymer (A-1) and 20 wt % of Ethylene-BasedPolymer (B-1). The results obtained are shown in Table 1a-1 and Table1a-2.

Comparative Example C1a(a)

Production of Polyethylene-Based Resin Composition C1a and film moldingwere performed in the same manner as in Example 1a(c) except that inExample 1a(c), a high-pressure radical process low-density polyethylene(LF240, produced by Japan Polyethylene Corporation; MFR=0.7 g/10 min,density: 0.924 g/cm³) was used in place of Ethylene-Based Polymer (B-1).The results obtained are shown in Table 1a-1 and Table 1a-2.

Comparative Example C1a(b)

Production of Polyethylene-Based Resin Composition C1b and film moldingwere performed in the same manner as in Example 1a(c) except that inExample 1a(c), a commercially available ethylene-based polymer having along-chain branch (CB2001, produced by Sumitomo Chemical Co., Ltd.;MFR=1.8 g/10 min, density: 0.918 g/cm³) was used in place ofEthylene-Based Polymer (B-1). The results obtained are shown in Table1a-1 and Table 1a-2.

Comparative Example C1a(c)

Production of Polyethylene-Based Resin Composition C1c and film moldingwere performed in the same manner as in (3) of Example 1a(a) except thatin Example 1a(a), Ethylene-Based Polymer (A-1) was used alone withoutusing Ethylene-Based Polymer (B-1). The results obtained are shown inTable 1a-1 and Table 1a-2.

Example 2a

Production of Polyethylene-Based Resin Composition 2 and film moldingwere performed in the same manner as in Example 1a(c) except that inExample 1a(c), a commercially available Ethylene-Based Polymer (A-2)produced using Magnesiumn.Titanium Composite Ziegler Catalyst (A-2)(UF230, produced by Japan Polyethylene Corporation: MFR=1.0 g/10 min,density: 0.921 g/cm³, ethylene.1-butene copolymer) was used in place ofEthylene-Based Polymer (A-1) produced by a metallocene catalyst. Theresults obtained are shown in Table 1a-1 and Table 1a-2.

Comparative Example 2a

Production of Polyethylene-Based Resin Composition C2 and film moldingwere performed in the same manner except that in Example 2a,Ethylene-Based Polymer (A-2) was used alone without using Ethylene-BasedPolymer (B-1). The results obtained are shown in Table 1a-1 and Table1a-2.

Example 3a(a) (1) Production of Ethylene-Based Polymer (B-3)[Preparation of Metallocene Catalyst B-3]

Solid Catalyst B-3 was obtained in the same manner as in (2) of Example1a(a) except that as the metallocene complex, 46.6 mg ofdimethylsilylene(cyclopentadienyl)(3-methylindenyl)zirconium dichlorideand 5.6 mg of rac-dimethylsilylenebis(indenyl)zirconium dichloride(produced by Wako Pure Chemical Industries, Ltd.) were used in place of51.8 mg of dimethylsilylene(cyclopentadienyl)(3-methylindenyl)zirconiumdichloride.

[Production of Ethylene.1-Hexene Copolymer]

Continuous gas-phase copolymerization of ethylene.1-hexene was performedin the same manner as in (2) of Example 1a(a) by using Solid CatalystB-3. That is, in a continuous gas-phase polymerization apparatus (innervolume: 100 L, diameter of fluidized bed: 10 cm, seed polymer offluidized bed (dispersant): 1.8 kg) set such that the temperature is 75°C., the molar ratio of hexene/ethylene is 0.007, the molar ratio ofhydrogen/ethylene is 2.5×10⁻³, the nitrogen concentration is 20 mol %and the total pressure is 0.8 MPa, polymerization was performed bykeeping the gas composition and the temperature constant whileintermittently feeding the solid catalyst at a rate of 0.18 g/hour.Also, in order to maintain the cleanliness in the system. 0.03 mol/L ofa triethylaluminum (TEA) solution diluted with hexane was fed at 7 ml/hrto a gas circulating line. As a result, the average production rate ofthe product polyethylene became 300 g/hour. After producing apolyethylene in a cumulative amount of 5 kg or more, the MFR and densityof the obtained Ethylene-Based Polymer (B-3) were 0.3 g/10 min and 0.921g/cm³, respectively.

(2) Production of Polyethylene-Based Resin Composition 3a

A polyethylene resin composed of 90 wt % of Ethylene-Based Polymer (A-1)produced in (1) of Example 1a(a) and 10 wt % of Ethylene-Based Polymer(B-3) obtained in (1) above was mixed and homogenized by a mixer.

The obtained mixture was melt-kneaded by a twin-screw extruder, and theextrudate was solidified and granulated. With respect to the finallyobtained Granular Polyethylene Resin Composition 3a, film moldabilityand film physical properties were evaluated by the above-describedmethod of molding a 30μ film. The results obtained are shown in Table2a-1 and Table 2a-2.

Example 4a(a) (1) Production of Ethylene-Based Polymer (B-4)[Preparation of Metallocene Catalyst B-4]

Solid Catalyst B-4 was obtained in the same manner as in (2) of Example1a(a) except that 52.5 mg of rac-ethylenebisindenylzirconium dichloride(produced by Strem Chemicals, Inc.) was used as the metallocene complexin place of 51.8 mg ofdimethylsilylene(cyclopentadienyl)(3-methylindenyl)zirconium dichlorideand reacted with methylaminoxane in a toluene solvent for 30 minutes inthe same manner as in (2) of Example 1a(a) and was further reacted for30 minutes by adding 10 ml of a separately prepared dehydrated toluenesolution containing 201 mg of N,N-dimethylaniliniumtetrakispentafluorophenylborate and thereafter, the catalyst wassupported on silica.

[Production of Ethylene.1-Hexene Copolymer]

An ethylene.1-hexene copolymer was produced using Solid Catalyst B-4.That is, 800 mL of isobutane, 22 mL of 1-hexene and 0.20 mmol oftriethylaluminum were added to a 2 L-volume autoclave with an inductionstirring device, the temperature was raised to 75° C., 130 mL of H₂ wasadded, and the ethylene partial pressure was kept at 1.4 MPa by furtherintroducing ethylene. Subsequently, 54 mg of Solid Catalyst B-4 wasinjected with nitrogen and after continuing the polymerization for 120minutes by keeping the ethylene partial pressure of 1.4 MPa and thetemperature of 75° C., the polymerization was stopped by adding ethanol.Incidentally, during the polymerization reaction, additional feeding ofH2 and 1-hexene was performed at feed rates proportional to the ethyleneconsumption rate. As a result, the molar ratio of H₂/C₂(hydrogen/ethylene) in the autoclave gas phase part at 10 minutes afterthe initiation of polymerization and at the completion of polymerizationwas 0.21% and 0.35%, respectively, and the amount of 1-hexeneadditionally fed was 28 mL. The amount of the thus-obtained EthylenePolymer (B-4) was 205 g, and the MFR and density thereof were 0.3 g/0min and 0.923 g/cm³, respectively.

(2) Production of Polyethylene-Based Resin Composition 4a

Polyethylene-Based Resin Composition 4a was produced and evaluated forfilm moldability and film physical properties in the same manner as in(2) of Example 3a(a) except for using Ethylene-Based Polymer (B-4) inplace of Ethylene-Based Polymer (B-3). The results obtained are shown inTable 2a-1 and Table 2a-2.

Example 5a(a) (1) Production of Ethylene-Based Polymer (B-5)[Preparation of Metallocene Catalyst B-5]

In a nitrogen atmosphere, 10 g of silica calcined at 600° C. for 5 hourswas put in a 200-ml two-neck flask and dried at reduced pressure with avacuum pump for 1 hour while heating the flask in an oil bath at 150° C.In a nitrogen atmosphere, 46 mg (0.1 mmol) of trisindenylzirconiumhydride and 118 mg (0.2 mmol) of trisbenzindenylzirconium hydride wereput in a separately prepared 100-ml two-neck flask and dissolved in 20ml of dehydrated toluene, and thereafter, 14.0 ml of a 20%methylaluminoxane/toluene solution produced by Albemarle was furtheradded at room temperature and stirred for 30 minutes. While heating the200-ml two-neck flask containing vacuum-dried silica in an oil bath at40° C. and stirring the contents, the entire amount of the toluenesolution above containing a reaction product of those two complexes andmethylaluminoxane was added and stirred at 40° C. for 1 hour. Whileheating the system at 40° C., the toluene solvent was removed bydistillation under reduced pressure to obtain Solid Catalyst B-5.

[Production of Ethylene.1-Hexene Copolymer]

Continuous gas-phase copolymerization of ethylene.1-hexene was performedin the same manner as in (2) of Example 1a(a) by using Solid CatalystB-5. That is, in a continuous gas-phase polymerization apparatus (innervolume: 100 L, diameter of fluidized bed: 10 cm, seed polymer offluidized bed (dispersant): 1.8 kg) set such that the temperature is 80°C., the molar ratio of hexene/ethylene is 0.020, the molar ratio ofhydrogen/ethylene is 4.7×10⁻⁴, the nitrogen concentration is 26 mol %and the total pressure is 0.8 MPa, polymerization was performed bykeeping the gas composition and the temperature constant whileintermittently feeding the solid catalyst at a rate of 0.19 g/hour.Also, in order to maintain the cleanliness in the system, 0.03 mol/L ofa triethylaluminum (TEA) solution diluted with hexane was fed at 7 ml/hrto a gas circulating line. As a result, the average production rate ofthe product polyethylene became 260 g/hour. After producing apolyethylene in a cumulative amount of 5 kg or more, the MFR and densityof the obtained Ethylene-Based Polymer (B-5) were 0.3 g/10 min and 0.922g/cm, respectively.

(2) Production of Polyethylene-Based Resin Composition 5a

Polyethylene-Based Resin Composition 5a was produced and evaluated forfilm moldability and film physical properties in the same manner as in(2) of Example 3a(a) except for using Ethylene-Based Polymer (B-5) inplace of Ethylene-Based Polymer (B-3). The results obtained are shown inTable 2a-1 and Table 2a-2.

Comparative Example C3a(a)

Production of Polyethylene-Based Resin Composition C3a and evaluation offilm moldability and film physical properties were performed in the samemanner as in Example 3a(2) except that a high-pressure radical processlow-density polyethylene (LF240, produced by Japan PolyethyleneCorporation) was used in place of Ethylene-Based Polymer (B-3). Theresults obtained are shown in Table 2a-1 and Table 2a-2.

Comparative Example C4a(a)

Production of Ethylene-based Polymer (B-C4) and Polyethylene-Based ResinComposition C4a and evaluation of film moldability and film physicalproperties were performed in the same manner as in Example 4a(a) exceptthat in (1) of Example 4a(a), N,N-dimethylaniliniumtetrakispentafluorophenylborate was not used. The results obtained areshown in Table 2a-1 and Table 2a-2.

Comparative Example C5a

Production of Polyethylene-Based Resin Composition C5 and evaluation offilm moldability and film physical properties were performed in the samemanner as in (2) of Example 3a(a) except that in Example 3a(a),Ethylene-Based Polymer (A-1) was used alone without using Ethylene-BasedPolymer (B-3). The results obtained are shown in Table 2a-1 and Table2a-2.

Comparative Example C6a

Production of Polyethylene-Based Resin Composition C6 and evaluation offilm moldability and film physical properties were performed in the samemanner as in (2) of Example 3a(a) except that in Example 5a(a),Ethylene-Based Polymer (B-5) was used alone without using Ethylene-BasedPolymer (A-1). The results obtained are shown in Table 2a-1 and Table2a-2.

Example 3a(b)

Production of Polyethylene-Based Resin Composition 3b and evaluation offilm moldability and film physical properties were performed in the samemanner as in (2) of Example 3a(a) except that in (2) of Example 3a(a),the mixing ratio of Ethylene-Based Polymer (A-1) and Ethylene-BasedPolymer (B-3) was changed to 80 wt %:20 wt %. The results obtained areshown in Table 2a-1 and Table 2a-2.

Example 4a(b)

Production of Polyethylene-Based Resin Composition 4b and evaluation offilm moldability and film physical properties were performed in the samemanner as in (2) of Example 4a(a) except that in (2) of Example 4a(a),the mixing ratio of Ethylene-Based Polymer (A-1) and Ethylene-BasedPolymer (B-4) was changed to 80 wt %:20 wt %. The results obtained areshown in Table 2a-1 and Table 2a-2.

Example 5a(b)

Production of Polyethylene-Based Resin Composition 5b and evaluation offilm moldability and film physical properties were performed in the samemanner as in (2) of Example 5a(a) except that in (2) of Example 5a(a),the mixing ratio of Ethylene-Based Polymer (A-1) and Ethylene-BasedPolymer (B-5) was changed to 80 wt %:20 wt %. The results obtained areshown in Table 2a-1 and Table 2a-2.

Comparative Example C3a(b)

Production of Polyethylene-Based Resin Composition C3b and evaluation offilm moldability and film physical properties were performed in the samemanner except that in Comparative Example C3a(a), the mixing ratio ofEthylene-Based Polymer (A-1) and high-pressure radical processlow-density polyethylene was changed to 80 wt %:20 wt %. The resultsobtained are shown in Table 2a-1 and Table 2a-2.

Comparative Example C7a

Production of Polyethylene-Based Resin Composition C7 and evaluation offilm moldability and film physical properties were performed in the samemanner as in Comparative Example C5a except that Ethylene-Based Polymer(A-3) produced in the same manner as in (1) of Example 1a(a) except forsetting the molar ratio of hexene/ethylene to 0.017 and setting themolar ratio of hydrogen/ethylene to 2.1×10⁻⁴ was used in place ofEthylene-Based Polymer (A-1). The results obtained are shown in Table2a-1 and Table 2a-2.

Example 5a(c)

Production of Polyethylene-Based Resin Composition 5c and evaluation offilm moldability and film physical properties were performed in the samemanner as in (2) of Example 5a(a) except that in (2) of Example 5a(a),the mixing ratio of Ethylene-Based Polymer (A-1) and Ethylene-BasedPolymer (B-5) was changed to 70 wt %:30 wt %. The results obtained areshown in Table 2a-1 and Table 2a-2.

Comparative Example C8a (1) Production of Ethylene-Based Polymer (A-4)

Ethylene-Based Polymer (A-4) was produced in the same manner as in (1)of Example 1a(a) except that the molar ratio of hexene/ethylene was setto 0.011 and the molar ratio of hydrogen/ethylene was set to 3.4×10⁻⁴.

(2) Production of Ethylene-Based Polymer (B-C8) [Preparation ofMetallocene Catalyst B-C8]

Solid Catalyst B-C8 was prepared in the same manner as in preparation ofMetallocene Catalyst B-1 in (2) of Example 1a(a) except that 95.6 mg ofdimethylsilylenebis[4-phenyl-2-(2-furyl)-indenyl]zirconium dichloridewas used in place ofdimethylsilylene(cyclopentadienyl)(3-methylindenyl)zirconium dichloride.Incidentally, dimethylsilylenebis[4-phenyl-2-(2-furyl)-indenyl]zirconiumdichloride was synthesized according to the procedure described inJP-T-2002-535339.

[Production of Ethylene.1-Hexene Copolymer]

An ethylene.1-hexene copolymer was produced using Solid Catalyst B-C8.That is. 800 mL of isobutane, 30 mL of 1-hexene and 2 mmol oftriethylaluminum were added to a 2 L-volume autoclave with an inductionstirring device, the temperature was raised to 75° C., 95 mL of H₂ wasadded, and the ethylene partial pressure was kept at 1.4 MPa by furtherintroducing ethylene. Subsequently, 27 mg of Solid Catalyst B-C8 wasinjected with nitrogen and after continuing the polymerization for 90minutes by keeping the ethylene partial pressure of 1.4 MPa and thetemperature of 75° C., the polymerization was stopped by adding ethanol.Incidentally, during the polymerization reaction, additional feeding ofH2 and 1-hexene was performed at feed rates proportional to the ethyleneconsumption rate. As a result, the molar ratio of H2/C2(hydrogen/ethylene) in the autoclave gas phase part at 10 minutes afterthe initiation of polymerization and at the completion of polymerizationwas 0.15% and 0.14%, respectively, and the amount of 1-hexeneadditionally fed was 19 mL. The amount of the thus-obtained EthylenePolymer (B-C8) was 113 g. and the MFR and density thereof were 0.05 g/10min and 0.894 g/cm³, respectively.

(3) Production of Polyethylene-Based Resin Composition C8

Polyethylene-Based Resin Composition C8 was produced and evaluated forfilm moldability and film physical properties in the same manner as inExample 5a(c) except that Ethylene-Based Polymer (A-4) was used in placeof Ethylene-Based Polymer (A-1) and Ethylene-Based Polymer (B-C8) wasused in place of Ethylene-Based Polymer (B-5). The results obtained areshown in Table 2a-1 and Table 2a-2.

Comparative Example C9a (1) Production of Ethylene-Based Polymer (A-4)

Continuous gas-phase copolymerization of ethylene.1-hexene was performedin the same manner as in (2) of Example 1a(a) using Solid Catalyst B-5.That is, in a continuous gas-phase polymerization apparatus (innervolume: 100 L, diameter of fluidized bed: 10 cm, seed polymer offluidized bed (dispersant): 1.8 kg) set such that the temperature is 85°C., the molar ratio of hexene/ethylene is 0.016, the molar ratio ofhydrogen/ethylene is 6.2×10⁻⁴, the nitrogen concentration is 30 mol %and the total pressure is 0.8 MPa, polymerization was performed bykeeping the gas composition and the temperature constant whileintermittently feeding the solid catalyst at a rate of 0.36 g/hour.Also, in order to maintain the cleanliness in the system, 0.03 mol/L ofa triethylaluminum (TEA) solution diluted with hexane was fed at 7 ml/hrto a gas circulating line. As a result, the average production rate ofthe product polyethylene became 400 g/hour. After producing apolyethylene in a cumulative amount of 5 kg or more, the MFR and densityof the obtained Ethylene-Based Polymer (B-5) were 5.9 g/10 min and 0.927g/cm³, respectively.

(2) Production of Polyethylene-Based Resin Composition C9

Polyethylene-Based Resin Composition C9 was produced and evaluated forfilm moldability and film physical properties in the same manner as inExample 5a(c) except that Ethylene-Based Polymer (A-5) was used in placeof Ethylene-Based Polymer (A-1) and Ethylene-Based Polymer (B-C8)produced in (2) of Comparative Example C8a was used in place ofEthylene-Based Polymer (B-5). The results obtained are shown in Table2a-1 and Table 2a-2.

Example 6a(a) (1) Production of Ethylene-Based Polymer (A-6)

Ethylene-Based Polymer (A-6) was produced in the same manner as in (1)of Example 1a(a) except that the molar ratio of 1-hexene/ethylene wasset to 0.011 and the molar ratio of hydrogen/ethylene was set to2.7×10⁻⁴.

(2) Production of Ethylene-Based Polymer (B-6)

Continuous gas-phase copolymerization of ethylene.1-hexene was performedin the same manner as in (1) of Example 5a(a). However, the temperaturewas 65° C., the molar ratio of hexene/ethylene was 0.025, the molarratio of hydrogen/ethylene was 9.3×10⁻⁴, the nitrogen concentration was24 mol % and the total pressure was 0.8 MPa. As a result, the averageproduction rate of the product polyethylene became 290 g/hour. Afterproducing a polyethylene in a cumulative amount of 5 kg or more, the MFRand density of the obtained Ethylene-Based Polymer (B-6) were 0.3 g/10min and 0.906 g/cm³, respectively.

(3) Production of Polyethylene-Based Resin Composition 6

Production of Polyethylene-Based Resin Composition 6 and evaluation offilm moldability and film physical properties were performed in the samemanner as in Example 5a(c) except that Ethylene-Based Polymer (A-6) andEthylene-Based Polymer (B-6) were used in place of Ethylene-BasedPolymer (A-1) and Ethylene-Based Polymer (B-5), respectively. Theresults obtained are shown in Table 3a-1 and Table 3a-2.

Comparative Example C10a(a)

Production of Polyethylene-Based Resin Composition C10 and evaluation offilm moldability and film physical properties were performed in the samemanner as in Comparative Example C5a except that Ethylene-Based Polymer(A-7) produced in the same manner as in (1) of Example 1a(a) except forsetting the molar ratio of 1-hexene/ethylene to 0.013 and setting themolar ratio of hydrogen/ethylene to 2.3×10⁻⁴ was used in place ofEthylene-Based Polymer (A-1). The results obtained are shown in Table3a-1 and Table 3a-2.

Example 7a(a) (1) Production of Ethylene-Based Polymer (A-7)

Ethylene-Based Polymer (A-7) produced by continuous gas-phasepolymerization using Magnesiumn.Titanium Composite Ziegler Catalyst(A-2) (MFR=1.5 g/10 min, density: 0.936 g/cm³, ethylene.1-butenecopolymer) was used.

(2) Production of Polyethylene-Based Resin Composition 7

Production of Polyethylene-Based Resin Composition 7 and evaluation offilm moldability and film physical properties were performed in the samemanner as in Example 3a(a) except that Ethylene-Based Polymer (A-7) andEthylene-Based Polymer (B-6) were used in place of Ethylene-BasedPolymer (A-1) and Ethylene-Based Polymer (B-3), respectively. Theresults obtained are shown in Table 3a-1 and Table 3a-2.

Comparative Example C11a(a)

Production of Polyethylene-Based Resin Composition C11 and evaluation offilm moldability and film physical properties were performed in the samemanner as in (2) of Example 7a(a) except that in Example 7a(a), the samehigh-pressure radical process low-density polyethylene as in ComparativeExample C1a(a) was used in place of Ethylene-Based Polymer (B-6) and themixing proportions of Ethylene-Based Polymer (A-7) and the high-pressureradical process low-density polyethylene were set to 80 wt % and 20 wt%. The results obtained are shown in Table 3a-1 and Table 3a-2.

Comparative Example C12a(a) (1) Production of Ethylene-Based Polymer(B-C9)

Continuous gas-phase copolymerization of ethylene.1-hexene was performedin the same manner as in (1) of Example 1a(a). However, the temperaturewas 65° C., the molar ratio of hexene/ethylene was 0.025 and the molarratio of hydrogen/ethylene was 2.6×10⁻⁴. As a result, the averageproduction rate of the product polyethylene became 320 g/hour. Afterproducing a polyethylene in a cumulative amount of 5 kg or more, the MFRand density of the obtained ethylene-based polymer were 1.0 g/10 min and0.906 g/cm³, respectively.

(2) Production of Polyethylene-Based Resin Composition C12

Production of Polyethylene-Based Resin Composition C12 was performed inthe same manner as in (2) of Example 7a(a) except that in ExampleC11a(a), a mixture of Ethylene-Based Polymer (B-C9) and a high-pressureradical process low-density polyethylene (produced by Japan PolyethyleneCorporation; MFR=0.8 g/10 min, density: 0.924 g/cm³) (mixing ratio: 66wt %:34 wt %) was used in place of Ethylene-Based Polymer (B-7) and themixing proportions of Ethylene-Based Polymer (A-7) and the mixture wereset to 62 wt % and 38 wt %.

That is, three components of Ethylene-Based Polymer (A-7),Ethylene-Based Polymer (B-C9) and the high-pressure radical processlow-density polyethylene were mixed and homogenized by a mixer, and theobtained mixture was melt-kneaded by a twin-screw extruder. Theextrudate was solidified and granulated, and with respect to the finallyobtained Granular Polyethylene Resin Composition C12, film moldabilityand film physical properties were evaluated by the above-describedmethod of molding a 30μ film. The results obtained are shown in Table3a-1 and Table 3a-2.

Comparative Example C13a(a)

Production of Polyethylene-Based Resin Composition C13 and evaluation offilm moldability and film physical properties were performed in the samemanner as in (2) of Example 7a(a) except that in Example C11a(a),Ethylene-Based Polymer (A-2) of Example 2a was used in place ofEthylene-Based Polymer (A-7) and the mixing proportions ofEthylene-Based Polymer (A-2) and the high-pressure radical processlow-density polyethylene were set to 90 wt % and 10 wt %. The resultsobtained are shown in Table 3a-1 and Table 3a-2.

Example 8a (1) Production of Ethylene-Based Polymer (B-8) [Preparationof Metallocene Catalyst B-8]

Solid Catalyst B-8 was obtained in the same manner as in (2) of Example1a(a) except that 68.7 mg ofdimethylsilylene(cyclopentadienyl)[4-(4-trimethylsilylphenyl)indenyl]zirconiumdichloride was used as the metallocene complex in place of 51.8 mg ofdimethylsilylene(cyclopentadienyl)(3-methylindenyl)zirconium dichloride.

[Production of Ethylene.1-Hexene Copolymer]

Continuous gas-phase copolymerization of ethylene.1-hexene was performedin the same manner as in (2) of Example 1a(a) using Solid Catalyst B-8.That is, in a continuous gas-phase polymerization apparatus (internalvolume: 100 L, diameter of fluidized bed: 10 cm, seed polymer offluidized bed (dispersant): 1.8 kg) which is set such that thetemperature is 75° C., the molar ratio of hexene/ethylene is 0.004, themolar ratio of hydrogen/ethylene is 5.5×10⁻³, the nitrogen concentrationis 20 mol % and the total pressure is 0.8 MPa, polymerization wasperformed by keeping the gas composition and the temperature constantwhile intermittently feeding the solid catalyst at a rate of 0.57g/hour. Also, in order to maintain the cleanliness in the system, 0.03mol/L of a triethylaluminum (TEA) solution diluted with hexane was fedat 12 ml/hr to a gas circulating line. As a result, the averageproduction rate of the product polyethylene became 288 g/hour. Afterproducing a polyethylene in a cumulative amount of 5 kg or more, the MFRand density of the obtained Ethylene-Based Polymer (B-8) were 0.2 g/10min and 0.920 g/cm³, respectively.

(2) Production of Polyethylene-Based Resin Composition 8a

A polyethylene resin composed of 80 wt % of a commercially availableEthylene-Based Polymer (A-2) produced using Magnesium.Titanium CompositeZiegler Catalyst (A-2) (UF230, produced by Japan PolyethyleneCorporation: MFR=1.0 g/10 min, density: 0.921 g/cm³, ethylene 1-butenecopolymer) and 20 wt % of Ethylene-Based Polymer (B-8) obtained in (1)above was mixed and homogenized by a mixer.

The obtained mixture was melt-kneaded by a twin-screw extruder, and theextrudate was solidified and granulated. With respect to the finallyobtained Granular Polyethylene Resin Composition 8a, film moldabilityand film physical properties were evaluated by the above-describedmethod of molding a 50μ film. The results obtained are shown in Table4a-1 and Table 4a-2.

Comparative Example 9a

Production of a polyethylene resin composition and evaluation of filmmolding were performed in the same manner as in Example 8a(2) exceptthat 90 wt % of the commercially available Ethylene-Based Polymer (A-2)and 10 wt % of Ethylene-Based Polymer (B-8) were used.

Comparative Example C14a

Production of Polyethylene-Based Resin Composition C14a and film moldingwere performed in the same manner as in Example 8a except that inExample 9a, a high-pressure radical process low-density polyethylene(LF240, produced by Japan Polyethylene Corporation; MFR=0.7 g/10 min,density: 0.924 g/cm³) was used in place of Ethylene-Based Polymer (B-8).The results obtained are shown in Table 4a-1 and Table 4a-2.

Comparative Example C15a

Production of Polyethylene-Based Resin Composition C15a and film moldingwere performed in the same manner as in Example 8a except that inExample 9a, a commercially available ethylene-based polymer having along-chain branch (CU5001, produced by Sumitomo Chemical Co., Ltd.;MFR=0.3 g/10 min, density: 0.922 g/cm³) was used in place ofEthylene-Based Polymer (B-8). The results obtained are shown in Table4a-1 and Table 4a-2.

TABLE 1a-1 Ethylene-Based Polymer (A) Ethylene-Based Polymer (B) Kind ofKind of λ_(max) Content Polymer- Den- Polymer- Den- (2.0)/ of izationMFR_(A) sity_(A) [Mw/ λ_(max) ization MFR_(B) sity_(B) [Mw/ λ_(max)λ_(max) λ_(max) g′ MW ≧10{circumflex over ( )}6 Catalyst g/10 min g/cm³Mn]_(A) (2.0) Catalyst g/10 min g/cm³ Mn]_(B) (2.0) (0.1) (0.1) Value %Example metal- 2.0 0.918 3.0 1.0 metal- 0.8 0.914 3.4 3.1 1.7 1.8 0.460.10 1a (a) locene locene Example 1a (b) Example 1a (c) Compar- high-0.7 0.924 3.9 4.3 2.6 1.7 0.26 2.94 ative pres- Example sure PE C1a (a)Compar- metal- 1.8 0.918 6.0 2.6 2.3 1.1 0.51 0.00 ative locene ExampleC1a (b) Compar- — — — — — — — — — ative Example C1a (c) Example Ziegler1.0 0.921 3.8 1.0 metal- 0.8 0.914 3.4 3.1 1.7 1.8 0.46 0.10 2a loceneCompar- — — — — — — — — — ative Example 2a

TABLE 1a-2 Polyethylene-Based Film Physical Properties Resin Composition1% Tensile Film Tear Tear Compositional Molding Resin Film Modulus inImpact Strength in Strength in Ratio Den- Temper- Pres- Thick- MDDirection Strength MD Direction TD Direction (A)/(A) + (B) MFR sityature sure ness (X) (Y) Haze (Z_(MD)) (Z_(TD)) Z_(MD)/ wt % g/10 ming/cm³ ° C. MPa μm MPa J/mm % N/mm N/mm Z_(TD) Example 95 1.9 0.918 17013.0 50 224 16.0 7.7 121 200 0.61 1a (a) Example 90 1.7 0.918 13.0 21115.6 6.5 87 219 0.40 1a (b) Example 80 1.5 0.917 12.9 204 13.7 4.8 56221 0.25 1a (c) Compar- 1.5 0.919 13.5 223 10.0 4.4 35 236 0.15 ativeExample C1a (a) Compar- 1.9 0.918 12.2 226 5.6 6.6 76 226 0.34 ativeExample C1a (b) Compar- 100 2.0 0.918 13.0 204 16.9 17.9 128 192 0.67ative Example C1a (c) Example 80 1.0 0.920 190 14.0 50 236 19.2 6.1 21165 0.13 2a Compar- 100 1.0 0.921 15.0 246 15.7 14.9 35 153 0.23 ativeExample 2a

TABLE 2a-1 Ethylene-Based Polymer (A) Ethylene-Based Polymer (B) Kind ofKind of λ_(max) Content Polymer- Den- Polymer- Den- (2.0)/ of izationMFR_(A) sity_(A) [Mw/ λ_(max) ization MFR_(B) sity_(B) [Mw/ λ_(max)λ_(max) λ_(max) g′ MW ≧10{circumflex over ( )}6 Catalyst g/10 min g/cm³Mn]_(A) (2.0) Catalyst g/10 min g/cm³ Mn]_(B) (2.0) (0.1) (0.1) Value %Example metal- 2.0 0.918 3.0 1.0 metal- 0.3 0.921 3.5 2.5 2.0 1.3 0.440.02 3a (a) locene locene Example metal- 0.3 0.923 5.1 2.0 1.6 1.3 0.460.46 4a (a) locene Example metal- 0.3 0.922 3.9 1.2 1.0 1.2 0.60 1.34 5a(a) locene Compar- high- 0.7 0.924 3.9 4.3 2.6 1.7 0.26 2.94 ative pres-Example sure PE C3a (a) Compar- metal- 0.5 0.925 6.1 5.0 4.6 1.1 0.492.19 ative locene Example C4a (a) Compar- — — — — — — — — — ativeExample C5a Compar- — — — — — metal- 0.3 0.922 3.9 2.3 1.6 1.4 0.60 1.34ative locene Example C6a Example metal- 2.0 0.918 3.0 1.0 metal- 0.30.921 3.5 2.5 2.0 1.3 0.44 0.02 3a (b) locene locene Example metal- 0.30.923 5.1 2.0 1.6 1.3 0.46 0.46 4a (b) locene Example metal- 0.3 0.9223.9 1.2 1.0 1.2 0.60 1.34 5a (b) locene Compar- high- 0.7 0.924 3.9 4.32.6 1.7 0.26 2.94 ative pres- Example sure PE C3a (b) Compar- 1.0 0.9202.9 1.0 — — — — — — — — — ative Example C7a Example metal- 2.0 0.918 3.01.0 metal- 0.3 0.922 3.9 1.2 1.0 1.2 0.60 1.34 5a (c) locene loceneCompar- metal- 4.5 0.931 2.5 1.0 metal-  0.05 0.894 3.3 1.0 1.0 1.0 0.910.29 ative locene locene Example C8a (a) Compar- metal- 5.9 0.927 2.72.2 ative locene Example C9a (a)

TABLE 2a-2 Polyethylene-Based Film Physical Properties Resin Composition1% Tensile Film Tear Tear Compositional Molding Resin Film Modulus inImpact Strength in Strength in Ratio Den- Temper- Pres- Thick- MDDirection Strength MD Direction TD Direction (A)/(A) + (B) MFR sityature sure ness (X) (Y) Haze (Z_(MD)) (Z_(TD)) Z_(MD)/ wt % g/10 ming/cm³ ° C. MPa μm MPa J/mm % N/mm N/mm Z_(TD) Example 90 1.2 0.918 17013.0 30 231 20.6 7.1 120 194 0.62 3a (a) Example 1.3 0.919 11.5 237 15.47.8 95 198 0.48 4a (a) Example 1.3 0.918 11.9 232 16.0 7.9 74 178 0.425a (a) Compar- 1.5 0.919 11.8 236 14.4 4.7 92 202 0.46 ative Example C3a(a) Compar- 1.4 0.920 12.0 244 17.6 10.0 112 186 0.60 ative Example C4a(a) Compar- 100 2.0 0.918 11.8 235 28.0 42.8 146 170 0.86 ative ExampleC5a Compar- 0 0.3 0.922 12.7 248 11.8 56.7 25 72 0.35 ative Example C6aExample 80 1.0 0.920 170 13.0 30 234 17.1 8.4 89 197 0.45 3a (b) Example1.1 0.922 11.0 250 13.0 6.7 83 207 0.40 4a (b) Example 1.1 0.921 12.0240 12.1 13.5 72 166 0.43 5a (b) Compar- 1.5 0.920 12.1 240 9.3 4.7 35283 0.12 ative Example C3a (b) Compar- 100 1.0 0.920 20.5 231 75.8 38.2124 142 0.87 ative Example C7a Example 70 0.7 0.922 170 12.2 30 259 25.914.7 67 146 0.46 5a (c) Compar- 0.7 0.920 17.8 241 28.9 14.6 82 184 0.45ative Example C8a (a) Compar- 0.7 0.917 15.0 223 37.8 25.5 31 142 0.22ative Example C9a (a)

TABLE 3a-1 Ethylene-Based Polymer (A) Ethylene-Based Polymer (B) Kind ofKind of λ_(max) Content Polymer- Den- Polymer- Den- (2.0)/ of izationMFR_(A) sity_(A) [Mw/ λ_(max) ization MFR_(B) sity_(B) [Mw/ λ_(max)λ_(max) λ_(max) g′ MW ≧10{circumflex over ( )}6 Catalyst g/10 min g/cm³Mn]_(A) (2.0) Catalyst g/10 min g/cm³ Mn]_(B) (2.0) (0.1) (0.1) Value %Example metal- 2.6 0.932 3.6 1.1 metal- 0.3 0.906 4.3 2.0 1.5 1.3 0.533.05 6a (a) locene locene Compar- metal- 1.8 0.927 2.7 1.1 — — — — — — —— — ative locene Example C10a (a) Example Ziegler 1.5 0.936 4.2 1.0metal- 0.3 0.906 4.3 2.0 1.5 1.3 0.53 3.05 7a (a) locene Compar- high-0.7 0.924 3.9 4.3 2.6 1.7 0.26 2.94 ative pressure PE Example C11a (a)Compar- metal- 0.8 0.913 4.0 3.8 2.5 1.5 0.74 0.54 ative locene +Example high- C12a (a) pressure PE Compar- 1.0 0.921 3.8 1.0 high- 0.70.924 3.9 4.3 2.6 1.7 0.26 2.94 ative pressure PE Example C13a (a)

TABLE 3a-2 Polyethylene-Based Film Physical Properties Resin Composition1% Tensile Film Tear Tear Compositional Molding Resin Film Modulus inImpact Strength in Strength in Ratio Den- Temper- Pres- Thick- MDDirection Strength MD Direction TD Direction (A)/(A) + (B) MFR sityature sure ness (X) (Y) Haze (Z_(MD)) (Z_(TD)) Z_(MD)/ wt % g/10 ming/cm³ ° C. MPa μm MPa J/mm % N/mm N/mm Z_(TD) Example 70 2.0 0.925 15016.0 30 276 9.8 15.9 22 142 0.15 6a (a) Compar- 100 1.8 0.927 21.2 31510.1 22.0 25 72 0.35 ative Example C10a (a) Example 90 1.1 0.933 18012.1 30 449 18.3 10.3 14 110 0.13 7a (a) Compar- 80 1.3 0.931 180 12.930 431 13.0 6.9 10 129 0.08 ative Example C11a (a) Compar- 62 1.2 0.928180 13.1 30 422 16.8 7.0 12 168 0.07 ative Example C12a (a) Compar- 900.9 0.922 180 13.8 30 248 19.2 7.8 14 149 0.09 ative Example C13a (a)

TABLE 4a-1 Ethylene-Based Polymer (A) Ethylene-Based Polymer (B) Kind ofKind of λ_(max) Content Polymer- Den- Polymer- Den- (2.0)/ of izationMFR_(A) sity_(A) [Mw/ λ_(max) ization MFR_(B) sity_(B) [Mw/ λ_(max)λ_(max) λ_(max) g′ MW ≧10{circumflex over ( )}6 Catalyst g/10 min g/cm³Mn]_(A) (2.0) Catalyst g/10 min g/cm³ Mn]_(b) (2.0) (0.1) (0.1) Value %Example Ziegler 1.0 0.921 3.8 1.0 metallocene 0.2 0.920 5.6 2.6 2.0 1.30.55 1.72 8a Example 9a Compar- high- 0.7 0.924 3.9 4.3 2.6 1.7 0.262.94 ative pressure PE Example C14a Compar- metallocene 0.3 0.922 7.23.5 3.6 1.0 0.48 1.00 ative Example C15a

TABLE 4a-2 Polyethylene-Based Film Physical Properties Resin Composition1% Tensile Film Tear Tear Compositional Molding Film Modulus in ImpactStrength in Strength in Ratio Den- Temper- Thick- MD Direction StrengthMD Direction TD Direction (A)/(A) + (B) MFR sity ature ness (X) (Y) Haze(Z_(MD)) (Z_(TD)) Z_(MD)/ wt % g/10 min g/cm³ ° C. μm MPa J/mm % N/mmN/mm Z_(TD) Example 8a 80 0.7 0.921 180 50 225 24.0 7.5 58 123 0.47Example 9a 90 0.8 0.921 230 22.0 6.3 68 118 0.58 Comparative 0.9 0.921231 21.0 6.4 47 95 0.49 Example C14a Comparative 0.8 0.921 235 22.0 8.462 109 0.57 Example C15a(Discussion on Results in Table 1a-1 and Table 1a-2)

Example 1a(a) to Comparative Example C1a(c) illustrate a case where anethylene.1-hexene copolymer produced using a general metallocenecatalyst is used for a film.

More specifically, in comparison with Comparative Example C1a(a) whereas a technique commonly employed at present in general on a commerciallevel, about 20% of a high-pressure radical polymerization processpolyethylene was blended to improve various physical properties of thecopolymer for a film, in Example 1a(c) where the ethylene-based polymer(B) according to the present invention was similarly blended in aproportion of 20%, reduction in the resin pressure was observed and themelt flowability was excellent. Also, as regards film physicalproperties, it is apparent that a film with excellent shock strength ofthe impact strength being larger by nearly 40%, despite the same levelof tensile modulus and haze, in other words, despite the same level ofelasticity and transparency of the film, could be obtained. InComparative Example C1a(b) where an ethylene-based copolymer that is along-chain branch-containing ethylene-based copolymer produced using atransition metal catalyst commercially available at present but is notthe ethylene copolymer (B) according to the present invention wasblended similarly in a proportion of about 20%, the effect of reducingthe resin pressure was obtained in the same way, but the impact strengthwas very small, resulting in a film having shock strength by farinferior to the film formed of the polyethylene-based resin compositionof the present invention, and the transparency was also not so excellentas obtained in the present invention.

Furthermore, in Example 1a(a) and Example 1a(b), the blending amount ofthe ethylene-based polymer (B) according to the present invention wassmaller than in the case above, and evidently, there was obtained aneffect of remarkably improving the transparency by reducing the hazevalue from about 18% to nearly 8% without deteriorating variousperformances, in terms of the resin pressure or the modulus or impactstrength of film, achieved in Comparative Example C1a(c) where theethylene-based polymer (B) was not blended,

Also, by the comparison between Example 2a and Comparative Example 2a, acase where the technique of the present invention is applied in using anethylene.1-butene copolymer produced with a general Ziegler catalyst fora film was illustrated.

More specifically, in Example 2a where similarly to the above-describedcase of a metallocene catalyst, 20% of the ethylene-based polymer (B)according to the present invention was blended with an ethylene.1-butenecopolymer produced using a Ziegler catalyst, there was produced anexcellent effect that while improving the resin pressure or the impactstrength of film, achieved in Comparative Example 2a where theethylene-based polymer (B) was not blended, an effect of remarkablyimproving the transparency by reducing the haze value from about 15% to6% is obtained.

(Discussion on Results in Table 2a-1 and Table 2a-2)

Example 3a(a) to Comparative Example C7a are experimental examplesplanned to clearly demonstrate that similarly to experimental examplesshown in Table 1a-1 and Table 1a-2, suitable performances are obtainedby applying the design technique of the polyethylene-based resincomposition of the present invention in using an ethylene.1-hexenecopolymer produced with a general metallocene catalyst for a film, andillustrate a case where a polymer produced using a different metallocenecatalyst was applied as the ethylene-based polymer (B) for use in thepresent invention.

More specifically, in Example 3a(a), Example 4a(a) and Example 5a(a),the performance of a film formed of a polyethylene-based resincomposition obtained by blending, in a proportion of 10%, each of theethylene-based polymers (B) according to the present invention producedusing different metallocene catalysts with the ethylene-based polymer(A) according to the present invention, and in Example 3a(b), Example4a(b) and Example 5a(b), the performance of a film obtained similarly byblending the same polymer in a proportion of 20%, were demonstrated bythe comparison with a case of blending a high-pressure polyethylene inthe same amount. In Examples using the polyethylene-based resincomposition according to the present invention, a tendency of the resinpressure being in the same level or lower was observed, and the meltflowability was excellent. As regards the film physical properties, onthe condition that the tensile modulus is the same, that is, the filmelasticity is the same, the transparency was slightly lower than in thecase of blending a high-pressure polyethylene but was improved to asufficiently practicable level and at the same time, the impact strengthwas enhanced by from nearly 10% to over 80%, clearly indicating that afilm excellent in the shock strength is obtained. In Comparative ExampleC4a(a) illustrating a case where an ethylene-based copolymer that is aknown long-chain branch-containing ethylene-based copolymer produced bya silica-supported methylalumoxane catalyst of a widely known bridgedbisindenylzirconocene complex and is not the ethylene-based polymer (B)according to the present invention was blended in the same manner, theimpact strength was slightly enhanced, but the haze was as bad as 10%and this may pose a problem for practical use in view of filmtransparency.

Example 5a(c) to Comparative Example C9a are experimental examplesplanned to compare Example 5a(c) using a combination of anethylene-based polymer (A) according to the present invention and anethylene-based polymer (B) according to the present invention, with eachof, as Comparative Examples, Comparative Example C8a where anethylene-based polymer (A) according to the present invention and anethylene-based polymer that is not the present invention in terms ofhaving no long-chain branch are combined, and Comparative Example C9awhere an ethylene-based polymer that is not the ethylene-based polymer(A) of the present invention in terms of having a long-chain branch andan ethylene-based polymer that is not the ethylene-based polymer (B) ofthe present invention in terms of having no long-chain branch arecombined. As compared with Example 5a(c) of the present invention, it isseen that in those Comparative Examples, the resin pressure was, on thecontrary, increased or the film transparency was not improved at all,which is not preferred.

(Discussion on Results in Table 3a-1 and Table 3a-2)

Example 6a(a) to Comparative Example C13a(a) are experimental examplesplanned to clearly demonstrate that similarly to experimental examplesshown in Table 1a-1 and Table 1a-2, suitable performances are obtainedby applying the design technique of the polyethylene-based resincomposition of the present invention in using an ethylene.1-hexenecopolymer produced with a general metallocene catalyst or an ethylene1-butene copolymer produced with a general Ziegler catalyst for a film.The polyethylene-based resin composition was designed to increase theratio of density_(A)/density_(B) by setting the density of theethylene-based polymer (B) to be lower than in Examples above, and itwas planned to prove that as a result of this design, a molded productvery excellent in the shock strength is obtained.

More specifically, in Example 6a(a) aiming at improving anethylene.1-hexene copolymer produced with a general metallocenecatalyst, as compared with Comparative Example C10a(a) singularly usingan ethylene.1-hexene copolymer having almost the same MFR, density andfilm impact strength, the resin pressure could be reduced by about 25%and furthermore, improvement of the transparency was revealed to berealizable, clearly demonstrating the superiority of thepolyethylene-based resin composition of the present invention.

In Example 7a(a) aiming at an ethylene.1-butene copolymer produced witha general Ziegler catalyst, when a low-density ethylene-based polymer(B) according to the present invention was blended, as compared withComparative Example C11a(a) as an example of a polyethylene-based resincomposition obtained by blending a high-pressure polyethylene and havingthe same MFR and density, the resin pressure or the tensile modulus offilm was slightly improved and the transparency was slightly lower thanin the case of blending a high-pressure polyethylene but improved to asufficiently practicable level. At the same time, the impact strengthwas enhanced by 40% or more, and it was apparent that a film withexcellent shock strength is obtained. The improvement effect for thishigh shock strength surpassed the shock strength in Comparative ExampleC12a(a) that is an example of a ternary blend composition developed withthe aim of achieving the same purpose.

These results clearly prove the reasonability and significance of theconfiguration requirements in the present invention and the superiorityof the present invention to conventional techniques.

Synthesis of Metallocene Compound Synthesis Example 1 Synthesis ofdimethylsilylene(4-tert-butylcyclopentadienyl)(indenyl)zirconiumdichloride (Metallocene Compound 11)

The compound was synthesized according to the procedure described inExample 1 of JP-A-09-87314.

Synthesis Example 2 Synthesis ofdimethylsilylene(cyclopentadienyl)(3-methylindenyl)zirconium dichloride(Metallocene Compound 12)

The compound was synthesized using 1-methylindene in place of indene inthe ligand synthesis by referring to the procedure described inMacromolecules 1995, 28, 3771-3778.

Synthesis Example 3 Synthesis ofdimethylsilylene(cyclopentadienyl)(indenyl)zirconium dichloride(Metallocene Compound 13)

The compound was synthesized according to the procedure described inMacromolecules 1995, 28, 3771-3778.

Synthesis Example 4 Synthesis ofdimethylsilylene(cyclopentadienyl)(3-tert-butylindenyl)zirconiumdichloride (Metallocene Compound 14)

The compound was synthesized using 1-tert-butylidene in place of indenein the ligand synthesis by referring to the procedure described inMacromolecules 1995, 28, 3771-3778.

Synthesis Example 5 Synthesis ofdimethylsilylene(cyclopentadienyl)(benz[e]indenyl)zirconium dichloride(Metallocene Compound 15)

The compound was synthesized using benz[e]indene in place of indene inthe ligand synthesis by referring to the procedure described inMacromolecules 1995, 28, 3771-3778.

Synthesis Example 6 Synthesis ofdimethylsilylene(cyclopentadienyl)(3-tert-butylcyclopentadienyl)zirconiumdichloride (Metallocene Compound 16)

The compound was synthesized using tert-butylcyclopentadiene in place ofindene in the ligand synthesis by referring to the procedure describedin Macromolecules 1995, 28, 3771-3778.

Synthesis Example 7 Synthesis ofdimethylsilylenebis(cyclopentadienyl)zirconium dichloride (MetalloceneCompound 17)

A commercial product was purchased from Wako Pure Chemical Industries,Ltd.

Synthesis Example 8 Synthesis ofdimethylsilylene(cyclopentadienyl)(2-(5-methyl-2-furyl)indenyl)zirconiumdichloride (Metallocene Compound 21)

The compound was synthesized according to the procedure described inExample 4 of JP-A-2012-025664.

Synthesis Example 9 Synthesis ofdimethylsilylene(cyclopentadienyl)(2-(5-methyl-2-furyl)-4-(4-tert-butylphenyl)indenyl)zirconiumdichloride (Metallocene Compound 22)

The compound was synthesized according to the procedure described inExample 3 of JP-A-2012-025664.

Synthesis Example 10 Synthesis ofracemi-dimethylsilylenebis(2-(5-trimethylsilyl-2-furyl)-4,5-dimethylcyclopentadienyl)zirconiumdichloride (Metallocene Compound 23)

The compound was synthesized according to the procedure described inExample 10 of JP-T-2002-535339.

Synthesis Example 11 Synthesis ofracemi-dimethylsilylenebis(2-(5-methyl-2-furyl)-4-(4-i-propylphenyl)indenyl)zirconiumdichloride (Metallocene Compound 24)

The compound was synthesized by preparing a ligand according to theprocedure described in Synthesis Example 1 of Japanese PatentApplication No. 2011-008562 and using zirconium tetrachloride in placeof hafnium tetrachloride.

Synthesis Example 12 Synthesis ofracemi-dimethylsilylenebis(2-(5-methyl-2-furyl)-4-(phenyl)indenyl)zirconiumdichloride (Metallocene Compound 25)

The compound was synthesized according to the procedure described inExample 1 of JP-A-2002-47313.

Synthesis Example 13 Synthesis ofisopropylidene(4-tert-butylcyclopentadienyl)(3-tert-butylindenyl)zirconiumdichloride (Metallocene Compound 26)

The compound was synthesized according to the procedure described inExample 1 of JP-A-05-148284.

Synthesis Example 14 Synthesis ofracemi-dimethylsilylenebis(indenyl)zirconium dichloride (MetalloceneCompound 27)

A commercial product was purchased from Wako Pure Chemical Industries,Ltd.

Synthesis Example 15 Synthesis ofracemi-dimethylsilylenebis(2-methyl-4-phenylindenyl)zirconium dichloride(Metallocene Compound 28)

The compound was synthesized according to the procedure described inOrganometallics 1994, 13, 954-963.

Synthesis Example 16 Synthesis ofracemi-isopropylidenebis(indenyl)zirconium dichloride (MetalloceneCompound 29)

The compound was synthesized according to the procedure described inExamples 1 and 3 of JP-A-09-20694.

Synthesis Example 17 Synthesis of racemi-ethylenebis(indenyl)zirconiumdichloride (Metallocene Compound 30)

A commercial product was purchased from Wako Pure Chemical Industries,Ltd.

Example 1b (1) Preparation of Solid Catalyst

In a nitrogen atmosphere, 5 g of silica calcined at 600° C. for 5 hourswas put in a 200-ml two-neck flask and dried at reduced pressure with avacuum pump for 1 hour while heating the flask in an oil bath at 150° C.In a nitrogen atmosphere, 22.7 mg of Metallocene Compound 11 and 23.9 mgof Metallocene Compound 21 were put in a separately prepared 100-mltwo-neck flask and dissolved in 13.4 ml of dehydrated toluene, and tothe resulting toluene solution of metallocene compounds, 8.6 ml of a 20%methylaluminoxane/toluene solution produced by Albemarle was added atroom temperature and stirred for 30 minutes. While heating the 200-mltwo-neck flask containing vacuum-dried silica in an oil bath at 40° C.and stirring the contents, the entire amount of the toluene solutionabove containing a reaction product of the metallocene compounds andmethylaluminoxane was added and stirred at 40° C. for 1 hour. Whilestill heating the system at 40° C., the toluene solvent was removed bydistillation under reduced pressure to obtain a solid catalyst.

(2) Production of Ethylene.1-Hexene Copolymer

An ethylene.1-hexene copolymer was produced using the solid catalystobtained in (1) Preparation of Solid Catalyst above.

That is, 800 mL of isobutane, 50 mL of 1-hexene and 0.20 mmol oftriethylahuninum were added to a 2 L-volume autoclave with an inductionstirring device, then, the temperature was raised to 75° C., and theethylene partial pressure was kept at 1.4 MPa by introducing ethylene.

Subsequently. 57 mg of the solid catalyst obtain in (1) above wasinjected with nitrogen and after continuing the polymerization for 60minutes by keeping the ethylene partial pressure of 1.4 MPa and thetemperature of 75° C., the polymerization was stopped by adding ethanol.

Incidentally, during the polymerization reaction, additional feeding of1-hexene was performed at a feed rate proportional to the ethyleneconsumption rate.

As a result, the molar ratio of H₂/C₂ (hydrogen/ethylene) in theautoclave gas phase part at 10 minutes after the initiation ofpolymerization and just prior to stopping of the polymerization was0.125% and 0.087%, respectively, and the amount of 1-hexene additionallyfed was 2.0 mL. The amount of the thus-obtained ethylene-based polymerwas 20.3 g. The polymerization results and the analysis results of thepolymer obtained are shown in Table 1b.

Example 2b Production of Ethylene-Based Polymer

An ethylene-based polymer was produced by the same method as in (2) ofExample 1b under the conditions shown in Table 1b by using a solidcatalyst obtained in the same manner as in (1) of Example 1b except forusing 30.5 mg of Metallocene Compound 22 in place of MetalloceneCompound 21.

The amount of the thus-obtained ethylene-based polymer was 43.3 g. Theresults are shown in Table 1b.

Example 3b (1) Preparation of Solid Catalyst

Preparation of Solid Catalyst was performed in the same manner as in (1)of Example 1b except for using 22.4 mg of Metallocene Compound 27 inplace of Metallocene Compound 21.

(2) Production of Ethylene.1-Hexene Copolymer

An ethylene.1-hexene copolymer was produced using the solid catalystobtained in (1) above.

That is, 50 g of polyethylene-made pellets subjected to full dehydrationand deoxidation and 0.20 mmol of triethylaluminum were added to astainless steel-made autoclave having an internal volume of 2 liter andhaving stirring and temperature control devices, and the temperature wasraised to 75° C. under stirring. After introducing 1.5 ml of 1-hexeneand ethylene until the partial pressure became 1.4 MPa, 80 mg of thesolid catalyst obtained above was injected with a nitrogen gas, andpolymerization was performed for 90 minutes.

Incidentally, during the polymerization reaction, additional feeding of1-hexene was performed at a feed rate proportional to the ethyleneconsumption rate. As a result, the molar ratio of H₂/C₂(hydrogen/ethylene) in the autoclave gas phase part at 10 minutes afterthe initiation of polymerization and just prior to stopping of thepolymerization was 0.065% and 0.076%, respectively, and the amount of1-hexene additionally fed was 5.5 mL.

Production of 35.0 g of polyethylene resulted. The polymerizationresults are shown together in Table 1b.

Example 4b Production of Ethylene-Based Polymer

An ethylene-based polymer was produced by the same method as in (2) ofExample 3 under the conditions shown in Table 1b by using a solidcatalyst obtained in the same manner as in (1) of Example 3b except forusing 9.1 mg of Metallocene Compound 11 and 35.9 mg of MetalloceneCompound 27.

The amount of the thus-obtained ethylene-based polymer was 28.5 g. Theresults are shown in Table 1b.

Example 5b Production of Ethylene-Based Polymer

An ethylene-based polymer was produced by the same method as in (2) ofExample 4b under the conditions shown in Table 1b by using a solidcatalyst obtained in the same manner as in (1) of Example 4b except forusing 50.3 mg of Metallocene Compound 28 in place of MetalloceneCompound 27.

Incidentally, 250 mL of H₂ and 1.5 ml of 1-hexene were added beforeinitiation of the polymerization and furthermore, during thepolymerization reaction, additional feeding of H₂ and 1-hexene wasperformed at feed rates proportional to the ethylene consumption rate.

The amount of the thus-obtained ethylene-based polymer was 42.0 g. Theresults are shown in Table 1b.

Comparative Example 1b Production of Ethylene-Based Polymer

An ethylene-based polymer was produced by the same method as in (2) ofExample 3b under the conditions shown in Table 1b by using a solidcatalyst obtained in the same manner as in (1) of Example 3b except forusing 45.5 mg of Metallocene Compound 11 and not using MetalloceneCompound 27.

The amount of the thus-obtained ethylene-based polymer was 49.5 g. Theresults are shown in Table 1b.

Comparative Example 2b Production of Ethylene-Based Polymer

An ethylene-based polymer was produced by the same method as in (2) ofExample 3b under the conditions shown in Table 1b by using a solidcatalyst obtained in the same manner as in (1) of Example 3b except fornot using Metallocene Compound 11 and using 44.9 mg of MetalloceneCompound 27.

The amount of the thus-obtained ethylene-based polymer was 22.5 g. Theresults are shown in Table 1b.

Comparative Example 3b Production of Ethylene-Based Polymer

An ethylene-based polymer was produced by the same method as inComparative Example 2b under the conditions shown in Table 1b.

The amount of the thus-obtained ethylene-based polymer was 44.5 g. Theresults are shown in Table 1b.

TABLE 54 [Table 1b] Polymerization Charge Catalyst Amount AmountEssential Essential of Polymer- of 1- Component (A-1b) Component (A-2b)Catalyst ization H2/C2 Hexene Kind μmol Kind μmol mg Method % ml Example1b Metallocene 50 Metallocene 50 57 S 0.11 50 Compound 11 Compound 21Example 2b Metallocene 50 Metallocene 50 50 S 0.55 50 Compound 11Compound 22 Example 3b Metallocene 50 Metallocene 50 80 G 0.07 1.5Compound 11 Compound 27 Example 4b Metallocene 20 Metallocene 80 107 G0.11 1.5 Compound 11 Compound 27 Example 5b Metallocene 20 Metallocene80 42 G 0.35 1.5 Compound 11 Compound 28 Comparative Metallocene 100 — —64 G 0.10 1.5 Example 1b Compound 11 Comparative — — Metallocene 100 62G 0.08 1.5 Example 2b Compound 27 Comparative — — Metallocene 100 74 G0.12 0.4 Example 3b Compound 27 Polymerization Addi- Analysis of Polymertional W_(c) Amount Activity λmax Value of 1- g/g MFR Den- (2.0)/ (MW ≧Hexene catalyst g/10 sity λ_(max) λ_(max) λmax g_(c)′ 10{circumflex over( )}6) ml hour min g/cm3 (0.1) (2.0) (0.1) Value % Example 1b 2.0 3571.4 0.932 1.2 3.6 3.0 0.45 2.2 Example 2b 8.0 866 2.7 0.925 1.0 1.9 1.90.60 1.2 Example 3b 5.5 292 12 0.930 2.5 7.8 3.1 0.39 1.2 Example 4b 4.0177 0.4 0.922 2.3 3.2 1.4 0.53 0.9 Example 5b 8.5 662 0.4 0.911 1.3 1.71.3 0.57 2.4 Comparative 9.5 516 38 0.927 — — — 0.36 0.8 Example 1bComparative 3.0 244 0.01 0.912 — — — 0.59 2.0 Example 2b Comparative 1.0299 0.2 0.937 1.0 1.1 1.1 0.69 0.7 Example 3b

As seen from Table 1b, in the case of an ethylene-based polymer obtainedusing only Metallocene Compound 11 of the component (A-1b), as inComparative Example 1b, despite low hydrogen polymerization conditions,it was difficult to sufficiently reduce MFR, and the W_(C) value wassmall, and in the case of an ethylene-based polymer obtained using onlyMetallocene Compound 27 of the component (A-2b), as in ComparativeExamples 2b and 3b, only a polymer where the g_(C)′ value is as large asabout 0.6 or more or the λ_(max)(2.0) or λ_(max)(2.0)/λ_(max)(0.1) issmall could be obtained, and enhancement of moldability could not bepromised. On the other hand, in the case of an ethylene-based polymerobtained by the same gas-phase polymerization by using both MetalloceneCompound 11 and Metallocene Compound 27, as in Example 3b, anethylene-based polymer where all of λ_(max)(2.0),λ_(max)(2.0)/λ_(max)(0.1), g_(C)′ value and W_(C) value were large toindicate well developing of a long-chain branched structure wasobtained, and it is understood that moldability was improved. In thecase of an ethylene-based polymer of Example 4b obtained by decreasingthe amount of Metallocene Compound 11 and increasing the amount ofMetallocene Compound 27, the λ_(max)(2.0), λ_(max)(2.0)/λ_(max)(0.1),g_(C)′ value and W_(C) value were smaller than in Example 3b and along-chain branched structure was slightly less developed, but it isunderstood that the moldability was excellent relative to ethylene-basedpolymers obtained by using respective metallocene compoundsindividually. In the case of an ethylene-based polymer of Example 5busing Metallocene Compound 28 as a different component (A-2b), the W_(C)value was greatly improved while maintaining the 1(2.0) (0.1) and g_(C)′value comparable to those in Example 4b. In the case of ethylene-basedpolymers of Example 1b and Example 2b where Metallocene Compound 21 orMetallocene Compound 22 was similarly used as a different component(A-2b) and a slurry polymerization method was performed, λ_(max)(2.0),λ_(max)(2.0)/λ_(max)(0.1) and W_(C) value were large enough and theg_(C)′ value was sufficiently small, and the polymer was proved to havea long-chain branched structure useful in enhancing the moldingcharacteristics.

Example 6b Production of Ethylene-Based Polymer

An ethylene-based polymer was produced by the same method as in (2) ofExample 3b under the conditions shown in Table 2b by using a solidcatalyst obtained in the same manner as in (1) of Example 3b except forusing 37.1 mg of Metallocene Compound 12 in place of MetalloceneCompound 11 and using 4.5 mg of Metallocene Compound 27.

The amount of the thus-obtained ethylene-based polymer was 38.5 g. Theresults are shown in Table 2b.

Example 7b Production of Ethylene-Based Polymer

An ethylene-based polymer was produced under the conditions shown inTable 2b by using a solid catalyst obtained in the same manner as inExample 6b except for using 4.3 mg of Metallocene Compound 29 in placeof Metallocene Compound 27.

The amount of the thus-obtained ethylene-based polymer was 31.0 g. Theresults are shown in Table 2b.

Comparative Example 4b Production of Ethylene-Based Polymer

An ethylene-based polymer was produced under the conditions shown inTable 2b by using a solid catalyst obtained in the same manner as inExample 6b except for using 41.3 mg of Metallocene Compound 12 and notusing Metallocene Compound 27.

The amount of the thus-obtained ethylene-based polymer was 31.0 g. Theresults are shown in Table 2b.

Comparative Example 5b Production of Ethylene-Based Polymer

An ethylene-based polymer was produced by the same method as inComparative Example 4b under the conditions shown in Table 2b.

The amount of the thus-obtained ethylene-based polymer was 42.5 g. Theresults are shown in Table 2b.

Example 8b Production of Ethylene-Based Polymer

An ethylene-based polymer was produced by the same method as in (2) ofExample 1b under the conditions shown in Table 2b by using a solidcatalyst obtained in the same manner as in (1) of Example 1b except forusing 39.1 mg of Metallocene Compound 13 in place of MetalloceneCompound 11 and using 1.5 mg of Metallocene Compound 25 in place ofMetallocene Compound 21.

Incidentally, 100 mL of H₂ and 40 ml of 1-hexene were added beforeinitiation of the polymerization and furthermore, during thepolymerization reaction, additional feeding of H₂ and 1-hexene wasperformed at feed rates proportional to the ethylene consumption rate.

The amount of the thus-obtained ethylene-based polymer was 48.5 g. Theresults are shown in Table 2b.

Example 9b Production of Ethylene-Based Polymer

An ethylene-based polymer was produced by the same method as in Example8b under the conditions shown in Table 2b.

The amount of the thus-obtained ethylene-based polymer was 48.5 g. Theresults are shown in Table 2b.

Example 10b Production of Ethylene-Based Polymer

An ethylene-based polymer was produced by the same method as in (2) ofExample 3b under the conditions shown in Table 2b by using the solidcatalyst obtained in Example 8b.

Incidentally, 370 mL of H₂ and 1.5 ml of 1-hexene were added beforeinitiation of the polymerization and furthermore, during thepolymerization reaction, additional feeding of H₂ and 1-hexene wasperformed at feed rates proportional to the ethylene consumption rate.

The amount of the thus-obtained ethylene-based polymer was 8.5 g. Theresults are shown in Table 2b.

Comparative Example 6b Production of Ethylene-Based Polymer

An ethylene-based polymer was produced under the conditions shown inTable 2b by using a solid catalyst obtained in the same manner as inExample 8b except for using 39.9 mg of Metallocene Compound 13 and notusing Metallocene Compound 25.

The amount of the thus-obtained ethylene-based polymer was 31.4 g. Theresults are shown in Table 2b.

Example 11b Production of Ethylene-Based Polymer

An ethylene-based polymer was produced under the conditions shown inTable 2b by using a solid catalyst obtained in the same manner as inExample 6b except for using 40.9 mg of Metallocene Compound 14 in placeof Metallocene Compound 12.

Incidentally, 60 mL of H₂ and 1.5 ml of 1-hexene were added beforeinitiation of the polymerization and furthermore, during thepolymerization reaction, additional feeding of H₂ and 1-hexene wasperformed at feed rates proportional to the ethylene consumption rate.

The amount of the thus-obtained ethylene-based polymer was 59.0 g. Theresults are shown in Table 2b.

Example 12b Production of Ethylene-Based Polymer

An ethylene-based polymer was produced under the conditions shown inTable 2b by using a solid catalyst obtained in the same manner as inExample 11 b except for using 35.9 mg of Metallocene Compound 15 inplace of Metallocene Compound 14 and using 9.0 mg of MetalloceneCompound 27. The amount of the thus-obtained ethylene-based polymer was30.5 g. The results are shown in Table 2b.

TABLE 55 [Table 2b] Polymerization Charge Catalyst Amount AmountEssential Essential of Polymer- of 1- Component (A-1b) Component (A-2b)Catalyst ization H2/C2 Hexene Kind μmol Kind μmol mg Method % ml Example6b Metallocene 90 Metallocene 10 60 G 0.11 1.5 Compound 12 Compound 27Example 7b Metallocene 90 Metallocene 10 56 G 0.17 1.5 Compound 12Compound 29 Comparative Metallocene 100 — — 44 G 0.12 1.5 Example 4bCompound 12 Comparative Metallocene 100 — — 181 G 0.18 1.5 Example 5bCompound 12 Example 8b Metallocene 98 Metallocene 2 175 S 0.39 40Compound 13 Compound 25 Example 9b Metallocene 98 Metallocene 2 175 S0.95 40 Compound 13 Compound 25 Example 10b Metallocene 98 Metallocene 249 G 0.48 2 Compound 13 Compound 25 Comparative Metallocene 100 — — 160S 0.20 40 Example 6b Compound 13 Example 11b Metallocene 90 Metallocene10 57 G 0.12 1.5 Compound 14 Compound 27 Example 12b Metallocene 80Metallocene 20 130 G 0.09 1.5 Compound 15 Compound 27 PolymerizationAddi- Analysis of Polymer tional W_(c) Amount Activity λmax Value of 1-g/g MFR Den- (2.0)/ (MW ≧ Hexene catalyst/ g/10 sity λ_(max) λ_(max)λmax g_(c)′ 10{circumflex over ( )}6) ml hour min g/cm3 (0.1) (2.0)(0.1) Value % Example 6b 6.0 426 0.2 0.919 1.4 1.9 1.4 0.45 0.4 Example7b 5.0 370 0.4 0.923 2.3 3.5 1.5 0.41 1.2 Comparative 4.0 470 0.2 0.9241.0 1.5 1.5 0.42 0.3 Example 4b Comparative 6.0 157 2.7 0.930 1.9 4.12.2 0.47 0.2 Example 5b Example 8b 8.0 278 0.3 0.911 2.0 3.4 1.7 0.490.7 Example 9b 8.0 278 3.9 0.913 1.7 5.9 3.5 0.50 0.2 Example 10b 1.0115 2.7 0.927 2.8 4.7 1.7 0.65 0.2 Comparative 7.2 196 8.1 0.929 2.6 6.52.5 0.84 1.5 Example 6b Example 11b 10 689 0.8 0.922 1.6 2.1 1.3 0.630.1 Example 12b 5.0 156 0.1 0.920 — — — 0.47 2.5

The results of the olefin polymerization catalyst of the presentinvention where each of Metallocene Compounds 12 to 15 as a metallocenedifferent from the component (A-1b) used in Table 1b was combined withMetallocene Compound 27 or the like used as the component (A-2b) inTable 1b are shown in Table 2b. Comparison with Comparative Example 4band Comparative Example 6b revealed that the ethylene-based polymersobtained are excellent in terms of λ_(max)(2.0),λ_(max)(2.0)/λ_(max)(0.1), g_(C)′ value and W_(C) value relative to apolymer using the component (A-1b) alone.

Example 13b Production of Ethylene-Based Polymer

An ethylene-based polymer was produced under the conditions shown inTable 3b by using a solid catalyst obtained in the same manner as inExample 1b except for using 36.4 mg of Metallocene Compound 16 in placeof Metallocene Compound 11 and using 6.1 mg of Metallocene Compound 22in place of Metallocene Compound 21.

The amount of the thus-obtained ethylene-based polymer was 11.0 g. Theresults are shown in Table 3b.

Example 14b Production of Ethylene-Based Polymer

An ethylene-based polymer was produced under the conditions shown inTable 3b by using a solid catalyst obtained in the same manner as inExample 13b except for using 6.8 mg of Metallocene Compound 23 in placeof Metallocene Compound 22.

The amount of the thus-obtained ethylene-based polymer was 30.0 g. Theresults are shown in Table 3b.

Example 15b Production of Ethylene-Based Polymer

An ethylene-based polymer was produced under the conditions shown inTable 3b by using a solid catalyst obtained in the same manner as inExample 13b except for using 8.5 mg of Metallocene Compound 24 in placeof Metallocene Compound 22.

The amount of the thus-obtained ethylene-based polymer was 20.0 g. Theresults are shown in Table 3b.

Example 16b Production of Ethylene-Based Polymer

An ethylene-based polymer was produced in the same manner as in Example15b under the conditions shown in Table 3b.

The amount of the thus-obtained ethylene-based polymer was 16.5 g. Theresults are shown in Table 3b.

Example 17b Production of Ethylene-Based Polymer

An ethylene-based polymer was produced under the conditions shown inTable 3b by using a solid catalyst obtained in the same manner as inExample 3b except for using 20.2 mg of Metallocene Compound 16 in placeof Metallocene Compound 11.

The amount of the thus-obtained ethylene-based polymer was 46.5 g. Theresults are shown in Table 3b.

Comparative Example 7b-1 Production of Ethylene-Based Polymer

An ethylene-based polymer was produced under the conditions shown inTable 3b by using a solid catalyst obtained in the same manner as inExample 17b except for using 40.5 mg of Metallocene Compound 16 and notusing Metallocene Compound 27.

The amount of the thus-obtained ethylene-based polymer was 42.0 g. Theresults are shown in Table 3b.

Comparative Example 7b-2 Production of Ethylene-Based Polymer

An ethylene-based polymer was produced under the conditions shown inTable 3b by using a solid catalyst obtained in the same manner as inExample 13b except for using 12.1 mg of Metallocene Compound 16 andusing 39.0 mg of Metallocene Compound 31 in place of MetalloceneCompound 22.

The amount of the thus-obtained ethylene-based polymer was 13.5 g. Theresults are shown in Table 3b.

TABLE 56 [Table 3b] Polymerization Catalyst Amount Charge AdditionalActivity Essential Essential of Polymer- Amount of Amount of g/g MFRComponent (A-1b) Component (A-2b) Catalyst ization H2/C2 1-Hexene1-Hexene catalyst/ g/10 Kind μmol Kind μmol mg Method % ml ml hour minExample 13b Metallocene 90 Metallocene 10 68 S 0.05 150 1.0 162 0.9Compound 16 Compound 22 Example 14b Metallocene 90 Metallocene 10 54 S0.13 150 6.5 550 0.8 Compound 16 Compound 23 Example 15b Metallocene 90Metallocene 10 43 S 0.29 50 3.0 461 6.2 Compound 16 Compound 24 Example16b Metallocene 90 Metallocene 10 47 S 0.10 50 2.0 354 1.2 Compound 16Compound 24 Example 17b Metallocene 50 Metallocene 50 58 G 0.13 1.5 7.5535 0.2 Compound 16 Compound 27 Comparative Metallocene 100 — — 62 G0.13 1.5 7.5 451 24 Example 7b-1 Compound 16 Comparative Metallocene 30Metallocene 70 71 S 0.08 60 2.0 189 0.3 Example 7b-2 Compound 16Compound 31 Polymer- Analysis of Polymer Amount of Amount of Amount ofAmount of ization W_(c) Value Soluble Soluble Soluble Soluble Densityλ_(max) λ_(max) λmax (2.0)/ g_(c)′ (MW ≧ Fraction at- Fraction atFraction at Fraction at g/cm3 (0.1) (2.0) λmax (0.1) Value 10{circumflexover ( )}6) % 15° C. [w %] 0° C. [w %] 20° C. [w %] 40° C. [w %] Example13b 0.917 1.0 2.0 2.0 0.44 1.7 0.4 0.4 1.8 7.7 Example 14h 0.913 1.0 1.81.8 0.68 0.3 0.4 0.4 1.3 10.2 Example 15b 0.917 1.0 1.9 1.9 0.79 0.1 3.74.8 17.2 30.7 Example 16b 0.925 1.7 2.6 1.5 0.69 0.7 1.3 1.5 4.4 15.2Example 17b 0.920 1.0 1.7 1.7 0.48 0.3 — — — — Comparative 0.930 3.1 4.71.5 0.38 0.1 0.3 0.8 2.2 5.2 Example 7b-1 Comparative 0.921 1.4 1.3 0.90.78 0.4 0.6 0.8 1.3 3.6 Example 7b-2

The results of the olefin polymerization catalyst of the presentinvention where Metallocene Compound 16 as a metallocene different fromthe component (A-1b) used in Table 1b or Table 2b was combined withMetallocene Compound 22, Metallocene Compound 27 or the like used as thecomponent (A-2b) in Table 1b are shown in Table 3b. Comparison withComparative Example 7b revealed that the ethylene-based polymersobtained are excellent in terms of λ_(max)(2.0),λ_(max)(2.0)/λ_(max)(0.1), g_(C)′ value and W_(C) value relative to apolymer using Metallocene 16 as the component (A-1b) alone.

Example 18b Production of Ethylene-Based Polymer

An ethylene-based polymer was produced under the conditions shown inTable 4b by using a solid catalyst obtained in the same manner as inExample 1b except for using 33.1 mg of Metallocene Compound 17 in placeof Metallocene Compound 11 and using 3.1 mg of Metallocene Compound 22in place of Metallocene Compound 21.

The amount of the thus-obtained ethylene-based polymer was 85.8 g. Theresults are shown in Table 4b.

Example 19b Production of Ethylene-Based Polymer

An ethylene-based polymer was produced under the conditions shown inTable 4b by using a solid catalyst obtained in the same manner as inExample 18b except for using 34.5 mg of Metallocene Compound 17 andusing 0.8 mg of Metallocene Compound 25 in place of Metallocene Compound22.

The amount of the thus-obtained ethylene-based polymer was 49.5 g. Theresults are shown in Table 4b.

Example 20b Production of Ethylene-Based Polymer

An ethylene-based polymer was produced by the same method as in (2) ofExample 3b under the conditions shown in Table 4b by using the solidcatalyst obtained in Example 19b.

The amount of the thus-obtained ethylene-based polymer was 25.5 g. Theresults are shown in Table 4b.

Example 21b Production of Ethylene-Based Polymer

An ethylene-based polymer was produced by the same method as in Example20b under the conditions shown in Table 4b.

The amount of the thus-obtained ethylene-based polymer was 23.5 g. Theresults are shown in Table 4b.

Example 22b Production of Ethylene-Based Polymer

An ethylene-based polymer was produced under the conditions shown inTable 4b by using a solid catalyst obtained in the same manner as inExample 20b except for using 32.4 mg of Metallocene Compound 17 andusing 3.5 mg of Metallocene Compound 26 in place of Metallocene Compound25.

The amount of the thus-obtained ethylene-based polymer was 22.9 g. Theresults are shown in Table 4b.

Example 23b Production of Ethylene-Based Polymer

An ethylene-based polymer was produced under the conditions shown inTable 4b by using a solid catalyst obtained in the same manner as inExample 18b except for using 32.4 mg of Metallocene Compound 17 andusing 3.1 mg of Metallocene Compound 27 in place of Metallocene Compound22.

The amount of the thus-obtained ethylene-based polymer was 72.0 g. Theresults are shown in Table 4b.

Example 24b Production of Ethylene-Based Polymer

An ethylene-based polymer was produced by the same method as in Example23b under the conditions shown in Table 4b.

The amount of the thus-obtained ethylene-based polymer was 47.1 g. Theresults are shown in Table 4b.

Example 25b Production of Ethylene-Based Polymer

An ethylene-based polymer was produced by the same method as in Example23b under the conditions shown in Table 4b.

The amount of the thus-obtained ethylene-based polymer was 100.2 g. Theresults are shown in Table 4b.

Example 26b Production of Ethylene-Based Polymer

An ethylene-based polymer was produced under the conditions shown inTable 4b by using a solid catalyst obtained in the same manner as inExample 24b except for using 33.5 mg of Metallocene Compound 17 andusing 1.8 mg of Metallocene Compound 27.

The amount of the thus-obtained ethylene-based polymer was 29.0 g. Theresults are shown in Table 4b.

Example 27b Production of Ethylene-Based Polymer

An ethylene-based polymer was produced under the conditions shown inTable 4b by using a solid catalyst obtained in the same manner as inExample 20b except for using 33.8 mg of Metallocene Compound 17 andusing 1.9 mg of Metallocene Compound 28 in place of Metallocene Compound25.

The amount of the thus-obtained ethylene-based polymer was 40.0 g. Theresults are shown in Table 4b.

Comparative Example 8b Production of Ethylene-Based Polymer

An ethylene-based polymer was produced under the conditions shown inTable 4b by using a solid catalyst obtained in the same manner as inExample 20b except for using 34.8 mg of Metallocene Compound 17 and notusing Metallocene Compound 25.

The amount of the thus-obtained ethylene-based polymer was 56.8 g. Theresults are shown in Table 4b.

Comparative Example 9b Production of Ethylene-Based Polymer

An ethylene-based polymer was produced under the conditions shown inTable 4b by using a solid catalyst obtained in the same manner as inExample 18b except for using 34.8 mg of Metallocene Compound 17 and notusing Metallocene Compound 22.

The amount of the thus-obtained ethylene-based polymer was 14.5 g. Theresults are shown in Table 4b.

Comparative Example 10b Production of Ethylene-Based Polymer

An ethylene-based polymer was in the same manner as in ComparativeExample 9b under the conditions shown in Table 4b.

The amount of the thus-obtained ethylene-based polymer was 79.4 g. Theresults are shown in Table 4b.

Comparative Example 11b Production of Ethylene-Based Polymer

An ethylene-based polymer was produced under the conditions shown inTable 4b by using a solid catalyst obtained in the same manner as inExample 23b except for using 44.9 mg of Metallocene Compound 27 and notusing Metallocene Compound 17.

The amount of the thus-obtained ethylene-based polymer was 54.9 g. Theresults are shown in Table 4b.

Comparative Example 12b Production of Ethylene-Based Polymer

An ethylene-based polymer was produced in the same manner as inComparative Example 11b under the conditions shown in Table 4b.

The amount of the thus-obtained ethylene-based polymer was 37.2 g. Theresults are shown in Table 4b.

Comparative Example 13b Production of Ethylene-Based Polymer

An ethylene-based polymer was produced under the conditions shown inTable 4b in the same manner as in Comparative Example 11b except forusing 41.8 mg of Metallocene Compound 30 in place of MetalloceneCompound 27.

The amount of the thus-obtained ethylene-based polymer was 129.6 g. Theresults are shown in Table 4b.

TABLE 57 [Table 4b] Polymerization Charge Catalyst Amount AmountEssential Essential of Polymer- of 1- Component (A-1b) Component (A-2b)Catalyst ization H2/C2 Hexene Kind μmol Kind μmol mg Method % ml Example18b Metallocene 95 Metallocene 5 353 S 0.77 50 Compound 17 Compound 22Example 19b Metallocene 99 Metallocene 1 276 S 0.73 40 Compound 17Compound 25 Example 20b Metallocene 99 Metallocene 1 255 G 0.08 1.5Compound 17 Compound 25 Example 21b Metallocene 99 Metallocene 1 255 G0.63 1.5 Compound 17 Compound 25 Example 22b Metallocene 93 Metallocene7 225 G 0.10 1.5 Compound 17 Compound 26 Example 23b Metallocene 93Metallocene 7 396 S 0.18 40 Compound 17 Compound 27 Example 24bMetallocene 93 Metallocene 7 390 S 0.12 20 Compound 17 Compound 27Example 25b Metallocene 93 Metallocene 7 422 S 0.10 80 Compound 17Compound 27 Example 26b Metallocene 96 Metallocene 4 381 S 0.09 20Compound 17 Compound 27 Example 27b Metallocene 97 Metallocene 3 397 G0.13 2.0 Compound 17 Compound 28 Comparative Metallocene 100 — — 533 G0.13 3.6 Example 8b Compound 17 Comparative Metallocene 100 — — 153 S0.10 80 Example 9b Compound 17 Comparative Metallocene 100 — — 686 S0.17 40 Example 10b Compound 17 Comparative — — Metallocene 100 68 S0.69 20 Example 11b Compound 27 Comparative — — Metallocene 100 75 S1.49 20 Example 12b Compound 27 Comparative — — Metallocene 100 137 S0.23 40 Example 13b Compound 30 Polymerization Addi- Analysis of Polymertional W_(c) Amount Activity λmax Value of 1- g/g MFR Den- (2.0)/ (MW ≧Hexene catalyst g/10 sity λ_(max) λ_(max) λmax g_(c)′ 10{circumflex over( )}6 ml hour min g/cm3 (0.1) (2.0) (0.1) Value % Example 18b 19 243 1.00.919 1.0 2.1 2.1 0.54 0.8 Example 19b 11 179 4.7 0.920 1.2 5.0 4.2 0.380.3 Example 20b 4.0 67 0.9 0.933 3.9 10.8 2.8 0.46 4.6 Example 21b 3.061 11 0.939 1.9 4.1 2.2 0.54 0.1 Example 22b 3.5 68 0.2 0.929 1.0 1.51.5 0.42 3.6 Example 23b 16 182 5.7 0.931 2.7 9.3 3.4 0.42 1.9 Example24b 4.5 121 4.7 0.946 1.0 3.7 3.7 0.43 2.6 Example 25b 25 238 1.6 0.9141.1 1.7 1.5 0.47 2.8 Example 26b 2.0 76 15 0.950 2.7 8.4 3.1 0.39 0.6Example 27b 8.0 67 0.6 0.921 4.4 7.3 1.7 0.44 5.5 Comparative 17 71 10680.919 — — — — — Example 8b Comparative 4.9 95 325 0.937 — — — — —Example 9b Comparative 16 116 309 0.941 — — — — — Example 10bComparative 7.0 808 0.2 0.930 1.0 1.0 1.0 0.55 1.9 Example 11bComparative 6.0 496 4.1 0.938 1.3 2.3 1.8 0.65 0.5 Example 12bComparative 37 946 0.5 0.922 4.6 5.0 1.1 0.49 2.2 Example 13b

The results of the olefin polymerization catalyst of the presentinvention where Metallocene Compound 17 as a metallocene different fromthe component (A-1b) used in Tables 1b to 3b was combined withMetallocene Compound 22, Metallocene Compound 25, Metallocene Compound27, Metallocene Compound 28 or the like used as the component (A-2b) inTable 1b are shown in Table 4b. Comparison with Comparative Example 8bto Comparative Example 12b revealed that the ethylene-based polymersobtained are excellent in terms of λ_(max)(2.0),λ_(max)(2.0)/λ_(max)(0.1), g_(C)′ value and W_(C) value relative to apolymer where Metallocene Compound 17 as the component (A-1b) orMetallocene Compound 27 as the component (A-2b) was used alone.Furthermore, comparison with Comparative Example 13 revealed that theethylene-based polymer obtained according to the present invention has amore proper value for the λ_(max)(2.0)/λ_(max)(0.1), g_(C)′ value andW_(C) value than the ethylene-based polymer obtained usingethylenebisindenylzirconium dichloride (Metallocene Compound 30) knownto provide for an excellent long-chain branched structure.

Example 28b Production of Ethylene-Based Polymer

An ethylene-based polymer was produced under the conditions shown inTable 5b by using the solid catalyst synthesized in Example 6b. That is,in a continuous gas-phase polymerization apparatus (internal volume: 100L, diameter of fluidized bed: 10 cm, seed polymer of fluidized bed(dispersant): 1.5 kg) which is set such that the molar ratio of1-hexene/ethylene is 0.007, the molar ratio of hydrogen/ethylene is2.5×10⁻³, the nitrogen concentration is 30 mol %, the total pressure is0.8 MPa and the temperature is 75° C., a hexane solution (0.03 mmol/ml)of triethylaluminum was fed at 7 ml/h and while keeping the gascomposition and the temperature constant, polymerization was performedby intermittently feeding the solid catalyst so as to achieve aproduction amount of about 300 g per hour. The activity was 336 g/(gcatalyst-hour). The results are shown in Table 5b.

Example 29b Production of Ethylene-Based Polymer

An ethylene-based polymer was produced under the conditions shown inTable 5 in the same manner as in Example 28b. The results are shown inTable 5b.

Example 30b Production of Ethylene-Based Polymer

An ethylene-based polymer was produced under the conditions shown inTable 5b in the same manner as in Example 28b except for setting thepolymerization temperature to 65° C. The results are shown in Table 5b.

Example 31b Production of Ethylene-Based Polymer

An ethylene-based polymer was produced under the conditions shown inTable 5b in the same manner as in Example 30b except for using 6.3 mg ofMetallocene Compound 28 in place of Metallocene Compound 27. The resultsare shown in Table 5b.

Comparative Example 14b Production of Ethylene-Based Polymer

An ethylene-based polymer having MFR of 0.8 g/10 min and a density of0.914 g/cm³ was obtained in the same manner as in (2) Production ofEthylene-Based Polymer (B-1) of Example 1a(a). The results are shown inTable 5b. While continuing the continuous operation, the molar ratio ofhexene/ethylene was increased from 0.012 so as to produce a lowerdensity ethylene-based polymer, as a result, despite no additionaladdition of hydrogen that is a molecular weight adjusting agent, MFRstarted increasing from 0.8 g/10 min with time, and it was difficult toproduce a low-MFR and low-density ethylene-based polymer as in Examples29b to 31b.

TABLE 5b Catalyst Polymerization Essential Component Essential ComponentAmount of Polymer- 1-Hexene/ (A-1b) (A-2b) Catalyst ization H2/C2 C2Kind μmol Kind μmol g/h Method % mol % Example 28b Metallocene 90Metallocene 10 0.18 G 0.25 0.7 Compound 12 Compound 27 Example 29bMetallocene 90 Metallocene 10 0.14 G 0.20 1.2 Compound 12 Compound 27Example 30b Metallocene 90 Metallocene 10 0.18 G 0.10 1.4 Compound 12Compound 27 Example 31b Metallocene 90 Metallocene 10 0.33 G 0.15 0.7Compound 12 Compound 28 Comparative Metallocene 100 — — 0.38 G 0.15 1.2Example 14b Compound 12 Polymerization Analysis of Polymer ActivityW_(c) g/g MFR Value TEA catalyst/ g/10 Density λ_(max) λ_(max) λ_(max)(2.0)/ g_(c)′ (MW ≧10{circumflex over ( )}6) mmol/h hour min g/cm3 (0.1)(2.0) λ_(max) (0.1) Value % Example 28b 0.21 336 0.3 0.921 2.0 2.5 1.30.44 0.02 Example 29b 0.23 620 0.7 0.913 1.8 2.7 1.5 0.56 0.01 Example30b 0.23 516 1.6 0.907 1.8 3.7 2.1 0.55 0.01 Example 31b 0.25 420 0.30.901 1.5 2.6 1.7 0.53 0.7 Comparative 0.23 320 0.8 0.914 1.7 3.1 1.80.46 0.1 Example 14b

(I) [Synthesis of Metallocene Compound] Metallocene Compound A Synthesisofdimethylsilylene(4-(4-trimethylsilyl-phenyl)-indenyl)(cyclopentadienyl)zirconiumdichloride (1-1) Synthesis of 4-(4-trimethylsilyl-phenyl)-indene

In a 500-ml flask, 10.0 g (51.5 mmol) of 4-trimethylsilylphenylboronicacid and 200 ml of dimethoethane were added to make a solution andthereafter, 27.3 g (128 mmol) of potassium phosphate, 100 ml of water,8.37 g (43.0 mmol) of 4-bromoindene, 0.22 g (0.86 mmol) oftriphenylphosphine, and 0.300 g (0.430 mmol) of PdCl₂(PPh₃)₂ were addedin sequence and stirred under reflux for 12 hours. After cooling to roomtemperature, 100 ml of water was added. The organic phase was separatedand then, the aqueous phase was extracted twice with 100 ml of ethylacetate. The obtained organic phases were mixed and washed with a salinesolution, and the resulting organic phase was dried by adding sodiumsulfate. Sodium sulfate was filtered, and the solvent was removed bydistillation under reduced pressure. The residue was purified on asilica gel column to obtain 9.0 g (yield: 79%) of4-(4-trimethylsilyl-phenyl)-indene as a yellow liquid.

(1-2) Synthesis of(4-(4-trimethylsilyl-phenyl)-indenyl)(cyclopentadienyl)dimethylsilane

In a 200-ml flask, 16.2 g (61.2 mmol) of4-(4-trimethylsilyl-phenyl)-indene and 100 ml of THF were added to makea solution and after cooling to −78° C., 29.4 ml (173.5 mmol) of ann-butyllithium/hexane solution (2.5M) was added. The system was returnedto room temperature and stirred for 4 hours. In a separately prepared300-ml flask, 14.8 ml (122 mmol) of dimethyldichlorosilane and 20 ml ofTHF were added to make a solution and after cooling to −78° C., thereaction solution obtained above was added. The system was returned toroom temperature and stirred for 12 hours. The volatile matter wasremoved by distillation under reduced pressure to obtain 21.8 g of ayellow solution. To this yellow solution, 80 ml of THF was added to makea solution, and 36.7 ml (73.5 mmol) of a CpNa/THF solution (2M) wasadded at −30° C. The system was returned to room temperature and stirredfor 1 hour and after adding 100 ml of ice water thereto, the solutionwas extracted twice with 100 ml of ethyl acetate. The obtained organicphases were mixed and washed with a saline solution, and the resultingorganic phase was dried by adding sodium sulfate. Sodium sulfate wasfiltered, and the solvent was removed by distillation under reducedpressure.

The residue was purified on a silica gel column to obtain 12.0 g (yield:51%) of(4-(4-trimethylsilyl-phenyl)-indenyl)(cyclopentadienyl)dimethylsilane asa yellow liquid.

(1-3) Synthesis ofdimethylsilylene(4-(4-trimethylsilyl-phenyl)-indenyl)(cyclopentadienyl)zirconiumdichloride

In a 300-ml flask, 1.20 g (3.00 mmol) of(4-(4-trimethylsilylphenyl)indenyl)(cyclopentadienyl)dimethylsilane and20 ml of diethyl ether were added, and the mixture was cooled to −70° C.Thereto, 2.60 ml (6.60 mmol) of a 2.5 mol/L n-butyllithium-n-hexanesolution was added dropwise and after the completion of dropwiseaddition, the system was returned to room temperature and stirred for 2hours. The solvent of the reaction solution was removed by distillationunder reduced pressure, and 30 ml of dichloromethane was added. Theresulting solution was cooled to −70° C. in a dry ice-methanol bath, and0.770 g (3.30 mmol) of zirconium tetrachloride was added thereto. Themixture was stirred one night while allowing it to gradually return toroom temperature and from a solution obtained by filtering the reactionsolution, the solvent was removed by distillation under reducedpressure, as a result, a yellow powder was obtained. This powder wasrecrystallized from 10 ml of toluene to obtain 0.500 g (yield: 31%) ofdimethylsilylene(4-(4-trimethyl-silylphenyl)indenyl)(cyclopentadienyl)zirconiumdichloride as a yellow crystal.

¹H-NMR Values (CDCl₃): δ0.21 (s, 3H), δ0.23 (s, 9H), δ0.43 (s, 3H),δ5.48 (m, 1H), δ5.51 (m, 1H), δ5.81 (d, 1H), δ6.60 (m, 1H), δ6.66 (m,1H), δ6.95 (dd, 1H), δ7.13 (s, 1H), δ7.39 (dd, 2H), δ7.57 (d, 2H), δ7.95(d, 2H).

Metallocene Compound B Synthesis ofdimethylsilylene(4-(4-chloro-phenyl)-indenyl)(cyclopentadienyl)zirconiumdichloride (2-1) Synthesis of 4-(4-chloro-phenyl)-indene

The synthesis was performed by the same procedure as in MetalloceneCompound A (1-1) by using 4-chlorophenylboronic acid in place of4-trimethylsilylphenylboronic acid in the synthesis of4-(4-trimethylsilyl-phenyl)-indene to obtain a white solid of4-(4-chloro-phenyl)-indene in a yield of 69%.

(2-2) Synthesis of(4-(4-chloro-phenyl)-indenyl)(cyclopentadienyl)dimethylsilane

The synthesis was performed by the same procedure as in MetalloceneCompound A (1-2) by using 4-(4-chloro-phenyl)-indene in place of4-(4-trimethylsilyl-phenyl)-indene to obtain a pale yellow solid of(4-(4-chloro-phenyl)-indenyl)(cyclopentadienyl)dimethylsilane in a yieldof 52%.

(2-3) Synthesis ofdimethylsilylene(4-(4-chloro-phenyl)-indenyl)(cyclopentadienyl)zirconiumdichloride

The synthesis was performed by the same procedure as in MetalloceneCompound A (1-3) by using(4-(4-chlorophenyl)indenyl)(cyclopentadienyl)dimethylsilane in place of(4-(4-trimethylsilylphenyl)indenyl)(cyclopentadienyl)dimethylsilane toobtaindimethylsilylene(4-(4-chloro-phenyl)-indenyl)(cyclopentadienyl)zirconiumdichloride as a yellow crystal.

¹H-NMR Values (CDCl₃): δ0.87 (s, 3H), δ1.08 (s, 3H), δ5.89 (m, 1H),δ5.94 (m, 1H), δ6.24 (d, 1H), δ6.78 (m, 1H), δ6.84 (m, 1H), δ7.12 (d,1H), δ7.19 (dd, 1H), δ7.39 (d, 1H), δ7.44 (m, 3H), δ7.61 (d, 2H).

Metallocene Compound C Synthesis ofdimethylsilylene(4-(2-(5-methyl)-furyl)-indenyl)(cyclopentadienyl)zirconiumdichloride (3-1) Synthesis of 4-(2-(5-methyl)-furyl)-indene

In a 500-ml flask, 2.52 g (30.7 mmol) of 2-methylfuran and 30 ml of THFwere added to make a solution and after cooling to −78° C., 14.7 ml(36.9 mmol) of an n-butyllithium-hexane solution (2.5M) was added. Thesystem was returned to room temperature and stirred for 4 hours. In aseparately prepared 300-ml flask. 4.18 g (30.7 mmol) of zinc chlorideand 10 ml of THF were added to make a suspension and after cooling to 0°C., the reaction solution obtained above was added. The system wasreturned to room temperature and stirred for 1 hour. Furthermore, in aseparately prepared 300 mil-volume flask, 0.35 g (1.84 mmol) ofcopper(I) iodide, 0.690 g (0.932 mmol) of Pd(dppf)Cl₂, 3.00 g (15.3mmol) of 4-bromoindene and 5 ml of DMA were added to make a suspension,and the reaction solution obtained above was added and stirred underreflux for 15 hours. After cooling to room temperature, 50 ml of waterwas added. The organic phase was separated and then, the aqueous phasewas extracted twice with 50 ml of ethyl acetate. The obtained organicphases were mixed and washed twice with 50 ml of water and washed oncewith 50 ml of a saline solution, and the resulting organic phase wasdried by adding sodium sulfate. Sodium sulfate was filtered, and thesolvent was removed by distillation under reduced pressure. The residuewas purified on a silica gel column to obtain 2.10 g (yield: 70%) of4-(2-(5-methyl)-furyl)-indene as a yellow liquid.

(3-2) Synthesis of(4-(2-(5-methyl)-furyl)-indenyl)(cyclopentadienyl)dimethylsilane

The synthesis was performed by the same procedure as in MetalloceneCompound A (1-2) by using 4-(2-(5-methyl)-furyl)-indene in place of4-(4-trimethylsilyl-phenyl)-indene to obtain a pale yellow solid of(4-(2-(5-methyl)-furyl)-indenyl)(cyclopentadienyl)dimethylsilane in ayield of 38%.

(3-3) Synthesis ofdimethylsilylene(4-(2-(5-methyl)-furyl)-indenyl)(cyclopentadienyl)zirconiumdichloride

The synthesis was performed by the same procedure as in MetalloceneCompound A (1-3) by using(4-(2-(5-methyl)-furyl)-indenyl)(cyclopentadienyl)dimethylsilane inplace of(4-(4-trimethylsilylphenyl)indenyl)(cyclopentadienyl)dimethylsilane toobtaindimethylsilylene(4-(2-(5-methyl)-furyl)-indenyl)(cyclopentadienyl)zirconiumdichloride as a yellow crystal (yield: 25%).

¹H-NMR Values (CDCl₃): δ0.00 (s, 3H), δ0.18 (s, 3H), δ1.79 (s, 3H),δ5.22 (m, 1H), δ5.32 (m, 1H), δ5.64 (m, 1H), δ5.72 (d, 1H), δ6.33 (m,1H), δ6.35 (m, 1H), δ6.70 (m, 2H), δ6.82 (d, 1H), δ7.43 (d, 1H), δ7.60(d, 1H).

Metallocene Compound D Synthesis ofdimethylsilylene(4-(4-methoxy-phenyl)-indenyl)(cyclopentadienyl)zirconiumdichloride (4-1) Synthesis of 4-(4-methoxy-phenyl)-indene

The synthesis was performed by the same procedure as in MetalloceneCompound A (1-1) by using 4-methoxyphenylboronic acid in place of4-trimethylsilylphenylboronic acid in the synthesis of4-(4-trimethylsilyl-phenyl)-indene to obtain a yellow liquid of4-(4-methoxy-phenyl)-indene in a yield of 890.

(4-2) Synthesis of(4-(4-methoxy-phenyl)-indenyl)(cyclopentadienyl)dimethylsilane

The synthesis was performed by the same procedure as in MetalloceneCompound A (1-2) by using 4-(4-methoxy-phenyl)-indene in place of4-(4-trimethylsilyl-phenyl)-indene to obtain a yellow liquid of(4-(4-methoxy-phenyl)-indenyl)(cyclopentadienyl)dimethylsilane in ayield of 35%.

(2-3) Synthesis ofdimethylsilylene(4-(4-methoxy-phenyl)-indenyl)(cyclopentadienyl)zirconiumdichloride

The synthesis was performed by the same procedure as in MetalloceneCompound A (1-3) by using(4-(4-methoxy-phenyl)indenyl)(cyclopentadienyl)dimethylsilane in placeof (4-(4-trimethylsilylphenyl)indenyl)(cyclopentadienyl)dimethylsilaneto obtaindimethylsilylene(4-(4-methoxy-phenyl)-indenyl)(cyclopentadienyl)zirconiumdichloride as a yellow crystal (yield: 54%).

¹H-NMR Values (CDCl₃): δ0.86 (s, 3H), δ1.07 (s, 3H), δ3.86 (s, 3H),δ5.88 (m, 1H), δ5.92 (m, 1H), δ6.22 (d, 1H), δ6.77 (m, 1H), δ6.84 (m,1H), δ7.00 (d, 2H), δ7.18 (m, 2H), δ7.40 (t, 2H), δ7.61 (d, 2H).

Metallocene Compound E Synthesis ofdimethylsilylene(4-phenylindenyl)(cyclopentadienyl)zirconium dichloride

The synthesis was performed by the same procedure as in MetalloceneCompound A (1-3) by using(4-phenylindenyl)(cyclopentadienyl)dimethylsilane in place of(4-(4-trimethylsilylphenyl)indenyl)(cyclopentadienyl)dimethylsilane toobtain dimethylsilylene(4-phenylindenyl)(cyclopentadienyl)zirconiumdichloride as a yellow crystal.

Metallocene Compound F Synthesis ofdimethylsilylene(3-methylindenyl)(cyclopentadienyl)zirconium dichloride

The synthesis was performed by the same procedure as in MetalloceneCompound A (1-3) by using(3-methylindenyl)(cyclopentadienyl)dimethylsilane in place of(4-(4-trimethylsilylphenyl)indenyl)(cyclopentadienyl)dimethylsilane toobtain dimethylsilylene(3-methylindenyl)(cyclopentadienyl)zirconiumdichloride as a yellow crystal.

Metallocene Compound G Synthesis ofdimethylsilylene(cyclopentadienyl)(indenyl)zirconium dichloride

The synthesis of dimethylsilylene(cyclopentadienyl)(indenyl)zirconiumdichloride was performed according to the procedure described inMacromolecules 1995, 28, 3771-3778.

Example 1-1 (1) Preparation of Solid Catalyst

In a nitrogen atmosphere, 5 g of silica calcined at 600° C. for 5 hourswas put in a 200-ml two-neck flask and dried at reduced pressure with avacuum pump for 1 hour while heating the flask in an oil bath at 150° C.In a nitrogen atmosphere, 68 mg of Metallocene Compound A was put in aseparately prepared 100-ml two-neck flask and dissolved in 13.4 ml ofdehydrated toluene, and to the resulting toluene solution of MetalloceneCompound A, 8.6 ml of a 20% methylaluminoxane/toluene solution producedby Albemarle was added at room temperature and stirred for 30 minutes.While heating the 200-ml two-neck flask containing vacuum-dried silicain an oil bath at 40° C. and stirring the contents, the entire amount ofthe toluene solution above containing a reaction product of MetalloceneCompound A and methylaluminoxane was added and stirred at 40° C. for 1hour. While still heating the system at 40° C., the toluene solvent wasremoved by distillation under reduced pressure to obtain a solidcatalyst.

(2) Production of Ethylene.1-Hexene Copolymer

An ethylene.1-hexene copolymer was produced using the solid catalystobtained in (1) Preparation of Solid Catalyst above.

That is, 30 ml of 1-hexene, 0.20 mmol of triethylaluminum, 200 ml ofhydrogen and 800 mL of isobutane were added to a 2 L-volume autoclavewith an induction stirring device, then, the temperature was raised to75° C., and the ethylene partial pressure was kept at 1.4 MPa byintroducing ethylene. Subsequently, 123 mg of the solid catalyst obtainin (1) Preparation of Solid Catalyst above was injected with nitrogen,and the polymerization was continued for 60 minutes by keeping theethylene partial pressure of 1.4 MPa and the temperature of 75° C.Incidentally, during the polymerization reaction, additional feeding of1-hexene was performed at a feed rate proportional to the ethyleneconsumption rate. The amount of 1-hexene fed additionally was 16.5 mL.The polymerization was stopped by adding ethanol. The amount of thethus-obtained ethylene.1-hexene copolymer was 130.3 g. Thepolymerization results are shown in Tables 5a-1 and 5a-2.

Example 1-2

An ethylene 1-hexene copolymer was produced in the same manner as inExample 1-1 except that 202 mg of the solid catalyst obtained in Example1-1 was used, 40 ml of 1-hexene and 150 ml of hydrogen were added, andthe amount of 1-hexene fed additionally was 9.0 mL. As a result, 55.0 gof an ethylene.1-hexene copolymer was produced. The polymerizationresults are shown in Tables 5a-1 and 5a-2.

Example 1-3

An ethylene.1-hexene copolymer was produced in the same manner as inExample 1-1 except that 206 mg of the solid catalyst obtained in Example1-1 was used and the amount of 1-hexene fed additionally was 9.0 mL. Asa result, 82.0 g of an ethylene.1-hexene copolymer was produced. Thepolymerization results are shown in Tables 5a-1 and 5a-2.

Example 1-4

An ethylene.1-hexene copolymer was produced in the same manner as inExample 1-1 except that 217 mg of the solid catalyst obtained in Example1-1 was used, 500 ml of hydrogen was added, and the amount of 1-hexenefed additionally was 6.0 mL. As a result, 54.8 g of an ethylene.1-hexenecopolymer was produced. The polymerization results are shown in Tables5a-1 and 5a-2.

Example 1-5

An ethylene.1-hexene copolymer was produced in the same manner as inExample 1-1 except that 204 mg of the solid catalyst obtained in Example1-1 was used, 640 ml of hydrogen was added, and the amount of 1-hexenefed additionally was 5.0 mL. As a result, 45.5 g of an ethylene.1-hexenecopolymer was produced. The polymerization results are shown in Tables5a-1 and 5a-2.

Comparative Example 1-1 (1) Preparation of Solid Catalyst

A solid catalyst was prepared in the same manner as in Example 1-1except for using 59 mg of Metallocene Compound E in place of 68 mg ofMetallocene Compound A.

(2) Production of Ethylene.1-Hexene Copolymer

An ethylene 1-hexene copolymer was produced in the same manner as inExample 1-1 except that 222 mg of the solid catalyst obtained in (1)Preparation of Solid Catalyst above was used in place of 123 mg of thesolid catalyst obtained in Example 1-1, 40 ml of 1-hexene was added, andthe amount of 1-hexene fed additionally was 13.5 mL. As a result, 111.8g of an ethylene.1-hexene copolymer was produced. The polymerizationresults are shown in Tables 5a-1 and 5a-2.

Comparative Example 1-2

An ethylene.1-hexene copolymer was produced in the same manner as inComparative Example 1-1 except that 218 mg of the solid catalystobtained in Comparative Example 1-1 was used, 70 ml of 1-hexene and 20ml of hydrogen were added, and the amount of 1-hexene fed additionallywas 1.5 mL. As a result, 24.0 g of an ethylene.1-hexene copolymer wasproduced. The polymerization results are shown in Tables 5a-1 and 5a-2.

Comparative Example 1-3 (1) Preparation of Solid Catalyst

A solid catalyst was prepared in the same manner as in Example 1-1except for using 52 mg of Metallocene Compound F in place of 68 mg ofMetallocene Compound A.

(2) Production of Ethylene.1-Hexene Copolymer

An ethylene.1-hexene copolymer was produced in the same manner as inExample 1-1 except that 236 mg of the solid catalyst obtained in (1)Preparation of Solid Catalyst above was used in place of 123 mg of thesolid catalyst obtained in Example 1-1, 70 ml of 1-hexene and 20 ml ofhydrogen were added, and the amount of 1-hexene fed additionally was18.0 mL. As a result, 146.0 g of an ethylene.1-hexene copolymer wasproduced. The polymerization results are shown in Tables 5a-1 and 5a-2.

Comparative Example 1-4 (1) Preparation of Solid Catalyst

A solid catalyst was prepared in the same manner as in Example 1-1except for using 50 mg of Metallocene Compound G in place of 68 mg ofMetallocene Compound A.

(2) Production of Ethylene.1-Hexene Copolymer

An ethylene.1-hexene copolymer was produced in the same manner as inExample 1-1 except that 160 mg of the solid catalyst obtained in (1)Preparation of Solid Catalyst above was used in place of 123 mg of thesolid catalyst obtained in Example 1-1. 40 ml of 1-hexene and 100 ml ofhydrogen were added, and the amount of 1-hexene fed additionally was 7.2mL. As a result, 31.4 g of an ethylene.1-hexene copolymer was produced.The polymerization results are shown in Tables 5a-1 and 5a-2.

Comparative Example 1-6 (1) Preparation of Solid Catalyst

A solid catalyst was prepared in the same manner as in Example 1-1except for using 64 mg of Metallocene Compound B in place of 68 mg ofMetallocene Compound A.

(2) Production of Ethylene.1-Hexene Copolymer

An ethylene.1-hexene copolymer was produced in the same manner as inExample 1-1 except that 233 mg of the solid catalyst obtained in (1)Preparation of Solid Catalyst above was used in place of 123 mg of thesolid catalyst obtained in Example 1-1, 40 ml of 1-hexene and 100 ml ofhydrogen were added, and the amount of 1-hexene fed additionally was 2.0mL. As a result, 29.2 g of an ethylene.1-hexene copolymer was produced.The polymerization results are shown in Tables 5a-1 and 5a-2.

Comparative Example 1-7

An ethylene.1-hexene copolymer was produced in the same manner as inExample 1-6 except that 270 mg of the solid catalyst obtained in Example1-6 was used, 70 ml of 1-hexene and 20 ml of hydrogen were added, andthe amount of 1-hexene fed additionally was 2.5 mL. As a result, 28.0 gof an ethylene.1-hexene copolymer was produced. The polymerizationresults are shown in Tables 5a-1 and 5a-2.

Example 1-8 (1) Preparation of Solid Catalyst

A solid catalyst was prepared in the same manner as in Example 1-1except for using 63 mg of Metallocene Compound D in place of 68 mg ofMetallocene Compound A.

(2) Production of Ethylene.1-Hexene Copolymer

An ethylene.1-hexene copolymer was produced in the same manner as inExample 1-1 except that 180 mg of the solid catalyst obtained in (1)Preparation of Solid Catalyst above was used in place of 123 mg of thesolid catalyst obtained in Example 1-1, 40 ml of 1-hexene and 100 ml ofhydrogen were added, and the amount of 1-hexene fed additionally was 9.0mL. As a result, 41.0 g of an ethylene.1-hexene copolymer was produced.The polymerization results are shown in Tables 5a-1 and 5a-2.

Example 1-9

An ethylene.1-butene copolymer was produced using the solid catalystobtained in (1) Preparation of Solid Catalyst of Example 1-1.

That is, 80 g of polyethylene-made pellets subjected to full dehydrationand deoxidation and 33 mg of triethylaluminum were introduced into astainless steel-made autoclave having an internal volume of 1 liter andhaving stirring and temperature control devices, and the temperature wasraised to 90° C. under stirring. After introducing ethylene containing10 wt % of 1-butene until the partial pressure became 2.0 MPa, 53 mg ofthe solid catalyst obtained above was injected with an argon gas, andpolymerization was continued for 60 minutes by keeping the ethylenepartial pressure of 2.0 MPa and the temperature of 90° C.

As a result, 14.6 g of an ethylene.1-butene copolymer was produced. Theobtained copolymer had FR of 26.2 and a density of 0.918 g/cm³. Thepolymerization results are shown in Tables 6a-1 and 6a-2.

Example 1-10

An ethylene.1-butene copolymer was produced in the same manner as inExample 1-9 except that 54 mg of the solid catalyst obtained in Example1-1 was used and 102 ml of hydrogen was added before the initiation ofpolymerization.

As a result, 10.8 g of an ethylene.1-butene copolymer was produced. Theobtained copolymer had FR of 13.3 and a density of 0.930 g/cm³, and thenumber of terminal double bonds was 0.40 bonds/1000 carbons. Thepolymerization results are shown in Tables 6a-1 and 6a-2.

Example 1-11

An ethylene.1-butene copolymer was produced in the same manner as inExample 1-9 except that 104 mg of the solid catalyst obtained in Example1-1 was used, 272 ml of hydrogen was added before the initiation ofpolymerization, ethylene containing 5 wt % of 1-butene was introduced inplace of ethylene containing 10 wt % of 1-butene, and the polymerizationwas performed for 56 minutes.

As a result, 25.8 g of an ethylene.1-butene copolymer was produced. TheFR of the obtained copolymer was 9.6. The polymerization results areshown in Tables 6a-1 and 6a-2.

Example 1-12

An ethylene.1-butene copolymer was produced in the same manner as inExample 1-9 except that 58 mg of the solid catalyst obtained in Example1-1 was used and 51 ml of hydrogen was added before the initiation ofpolymerization.

As a result, 11.1 g of an ethylene.1-butene copolymer was produced. TheFR of the obtained copolymer was 25.7. The polymerization results areshown in Tables 6a-1 and 6a-2.

Example 1-13

An ethylene.1-butene copolymer was produced in the same manner as inExample 1-9 except that 55 mg of the solid catalyst obtained in Example1-1 was used and 153 ml of hydrogen was added before the initiation ofpolymerization.

As a result, 10.4 g of an ethylene.1-butene copolymer was produced. Thepolymerization results are shown in Tables 6a-1 and 6a-2.

Comparative Example 1-5

An ethylene.1-butene copolymer was produced in the same manner as inExample 1-9 except that 60 mg of the solid catalyst obtained in (1)Preparation of Solid Catalyst of Comparative Example 1-1 was used inplace of 53 mg of the solid catalyst obtained in Example 1-1.

As a result, 13.2 g of an ethylene.1-butene copolymer was produced. Thedensity of the obtained copolymer was 0.935 g/cm³, and the number ofterminal double bonds was 0.30 bonds/1000 carbons. The polymerizationresults are shown in Tables 6a-1 and 6a-2.

Example 1-14

An ethylene.1-butene copolymer was produced in the same manner as inExample 1-9 except that 205 mg of the solid catalyst obtained in Example1-6 was used in place of 53 mg of the solid catalyst obtained in Example1-1 and 34 ml of hydrogen was added before the initiation ofpolymerization.

As a result, 29.1 g of an ethylene.1-butene copolymer was produced. Thedensity of the obtained copolymer was 0.936 g/cm³, and the number ofterminal double bonds was 0.40 bonds/1000 carbons. The polymerizationresults are shown in Tables 6a-1 and 6a-2.

Example 1-15

An ethylene.1-butene copolymer was produced in the same manner as inExample 1-9 except that 208 mg of the solid catalyst obtained in Example1-6 was used in place of 53 mg of the solid catalyst obtained in Example1-1 and 17 ml of hydrogen was added before the initiation ofpolymerization.

As a result, 25.8 g of an ethylene.1-butene copolymer was produced. Thedensity of the obtained copolymer was 0.936 g/cm³, and the number ofterminal double bonds was 0.40 bonds/1000 carbons. The polymerizationresults are shown in Tables 6a-1 and 6a-2.

Example 16 (1) Preparation of Solid Catalyst

A solid catalyst was prepared in the same manner as in Example 1-1except for using 60 mg of Metallocene Compound C in place of 68 mg ofMetallocene Compound A.

(2) Production of Ethylene.1-Butene Copolymer

An ethylene.1-butene copolymer was produced in the same manner as inExample 1-9 except that 203 mg of the solid catalyst obtained in (1)Preparation of Solid Catalyst above was used in place of 53 mg of thesolid catalyst obtained in Example 1-1 and the polymerization wasperformed for 47 minutes.

As a result, 29.5 g of an ethylene.1-butene copolymer was produced. TheFR of the obtained copolymer was 9.4. The polymerization results areshown in Tables 6a-1 and 6a-2.

TABLE 59 [Table 5a-1] Catalyst Component (A) Component (B) Component (C)Amount Metal- Amount Amount Amount of Solid locene Used Used UsedCatalyst Compound (mmol) Compound (mmol) Compound (g) (g) Example 1-1 A0.00238 MAO 0.48 silica 0.095 0.123 Example 1-2 A 0.00389 MAO 0.78silica 0.156 0.202 Example 1-3 A 0.00397 MAO 0.79 silica 0.159 0.206Example 1-4 A 0.00418 MAO 0.84 silica 0.167 0.217 Example 1-5 A 0.00393MAO 0.79 silica 0.157 0.204 Comparative E 0.00428 MAO 0.86 silica 0.1710.222 Example 1-1 Comparative E 0.00420 MAO 0.84 silica 0.168 0.218Example 1-2 Comparative F 0.00455 MAO 0.91 silica 0.182 0.236 Example1-3 Comparative G 0.00309 MAO 0.62 silica 0.124 0.160 Example 1-4Example 1-6 B 0.00448 MAO 0.90 silica 0.179 0.233 Example 1-7 B 0.00520MAO 1.04 silica 0.208 0.270 Example 1-8 D 0.00346 MAO 0.69 silica 0.1380.180 Polymerization Conditions Comonomer Addi- C2 Polymer- HydrogenInitial tional Temp- Partial ization TEA H2/C2 Charge Amount eraturePressure Time (mmol) Solvent (%) (ml) (ml) (° C.) (MPa) (min) Example1-1 0.20 isobutane 0.39 30.0 16.5 75 1.4 60 Example 1-2 0.20 isobutane0.31 40.0 9.0 75 1.4 60 Example 1-3 0.20 isobutane 0.43 30.0 9.0 75 1.460 Example 1-4 0.20 isobutane 1.16 30.0 6.0 75 1.4 60 Example 1-5 0.20isobutane 1.55 30.0 5.0 75 1.4 60 Comparative 0.20 isobutane 0.31 40.013.5 75 1.4 60 Example 1-1 Comparative 0.20 isobutane 0.09 70.0 1.5 751.4 60 Example 1-2 Comparative 0.20 isobutane 0.16 70.0 18.0 75 1.4 60Example 1-3 Comparative 0.20 isobutane 0.20 40.0 7.2 75 1.4 60 Example1-4 Example 1-6 0.20 isobutane 0.11 40.0 2.0 75 1.4 60 Example 1-7 0.20isobutane 0.07 70.0 2.5 75 1.4 60 Example 1-8 0.20 isobutane 0.20 40.09.0 75 1.4 60 Metallocene Compound A

B

C

D

E

F

G

TABLE 5a-2 Catalyst Results Component (A) Activity MFR MetalloceneAmount Used Yield (g-PE/ (g/10 Density λmax λmax λmax (2.0)/ Compound(mmol) (g) g-Cat/hr) min) FR (g/cm3) (2.0) (0.1) λmax (0.1) Example 1-1A 0.00238 130.3 576 0.5 22.4 0.914 1.6 1.0 1.6 Example 1-2 A 0.0038955.0 272 0.9 16.7 0.909 1.7 1.1 1.6 Example 1-3 A 0.00397 82.0 398 0.230.5 0.914 4.5 3.0 1.5 Example 1-4 A 0.00418 54.8 253 4.1 15.6 0.92411.4  6.7 1.7 Example 1-5 A 0.00393 45.5 223 17.7 10.7 0.921 9.3 2.5 3.8Comparative E 0.00428 111.8 503 1.1 17.4 0.914 1.4 1.0 1.4 Example 1-1Comparative E 0.00420 24.0 110 8.5 5.9 0.907 6.4 1.2 5.5 Example 1-2Comparative F 0.00455 146.0 618 3.2 13.4 0.920 3.8 1.7 2.2 Example 1-3Comparative G 0.00309 31.4 196 8.1 9.5 0.929 6.5 2.6 2.5 Example 1-4Example 1-6 B 0.00448 29.2 125 0.3 20.6 0.924 — — — Example 1-7 B0.00520 28.0 104 4.8 8.1 0.917 3.5 1.3 2.8 Example 1-8 D 0.00346 41.0228 19.2 9.4 0.934 — — — Results Amount of Amount of Amount of Amount ofSoluble Soluble Soluble Soluble W_(c) Fraction Fraction FractionFraction g_(c)′ Value at −15° C. at 0° C. at 20° C. at 40° C. Mw ×10⁴Mw/Mn Value (MW ≧10{circumflex over ( )}6) [wt %] [wt %] [wt %] [wt %]Example 1-1 12.9 7.4 0.41 4.5 0.3 0.5 1.6 4.5 Example 1-2 13.1 7.5 0.425.5 0.3 0.5 1.7 7.3 Example 1-3 15.3 9.2 0.42 5.8 0.3 0.4 1.4 4.0Example 1-4 7.9 8.0 0.44 2.0 0.6 0.7 1.4 3.8 Example 1-5 5.9 6.8 0.450.9 1.0 1.2 2.3 7.4 Comparative 10.4 7.4 0.42 2.2 1.2 1.6 2.9 5.8Example 1-1 Comparative 10.2 6.3 0.60 2.9 2.1 2.5 4.1 13.0  Example 1-2Comparative 6.9 4.3 0.50  0.07 0.4 0.7 1.4 3.7 Example 1-3 Comparative5.8 3.7 — — — — — — Example 1-4 Example 1-6 14.0 7.7 0.41 5.0 0.4 0.82.2 4.4 Example 1-7 10.3 6.1 0.45 3.0 0.7 1.0 2.5 9.7 Example 1-8 — — —— — — — —

TABLE 61 [Table 6a-1] Catalyst Component (A) Component (B) Component (C)Amount Metal- Amount Amount Amount of Solid locene Used Used UsedCatalyst Example Compound (mmol) Compound (mmol) Compound (g) (g)Example 1-9 A 0.00103 MAO 0.21 silica 0.041 0.053 Example 1-10 A 0.00105MAO 0.21 silica 0.042 0.054 Example 1-11 A 0.00202 MAO 0.40 silica 0.0810.104 Example 1-12 A 0.00113 MAO 0.23 silica 0.045 0.058 Example 1-13 A0.00107 MAO 0.21 silica 0.043 0.055 Comparative E 0.00116 MAO 0.23silica 0.046 0.060 Example 1-5 Example 1-14 B 0.00398 MAO 0.90 silica0.159 0.205 Example 1-15 B 0.00404 MAO 0.81 silica 0.162 0.208 Example1-16 C 0.00394 MAO 0.79 silica 0.158 0.203 Polymerization ConditionsComonomer Addi- C2 Polymer- Hydrogen Initial tional Temper- Partialization TEA H2/C2 Charge Amount ature Pressure Time Example (mmol)Solvent (%) (ml) (ml) (° C.) (MPa) (min) Example 1-9 0.30 gas 0.04 C4/C2= 5.0 mol % 90 2.0 60 phase Example 1-10 0.30 gas 0.36 C4/C2 = 5.0 mol %90 2.0 60 phase Example 1-11 0.30 gas 0.78 C4/C2 = 2.5 mol % 90 2.0 56phase Example 1-12 0.30 gas 0.20 C4/C2 = 5.0 mol % 90 2.0 60 phaseExample 1-13 0.30 gas 0.41 C4/C2 = 5.0 mol % 90 2.0 60 phase Comparative0.30 gas 0.36 C4/C2 = 5.0 mol % 90 2.0 60 Example 1-5 phase Example 1-140.30 gas 0.11 C4/C2 = 5.0 mol % 90 2.0 60 phase Example 1-15 0.30 gas0.03 C4/C2 = 5.0 mol % 90 2.0 60 phase Example 1-16 0.30 gas 0.06 C4/C2= 5.0 mol % 90 2.0 47 phase Metallocene Compound A

B

C

D

E

F

G

TABLE 6a-2 Catalyst Results Component (A) Activ- Terminal Metal- ityDen- λmax Double locene Amount (g-PE/ MFR sity Melting (2.0)/ Bond Com-Used Yield g-Cat/ (g/10 (g/ Point λmax λmax λmax Mw Mw/ (bonds/ g_(c)′W_(c) Value Example pound (mmol) (g) hr) min) FR cm3) (° C.) (2.0) (0.1)(0.1) ×10⁴ Mn 1000C) Value (MW ≧10{circumflex over ( )}6) Example A0.00103 14.6 275 0.05 26.2 0.918 104.5 — — — 20.4 5.7 — — — 1-9 ExampleA 0.00105 10.8 200 1.7 13.3 0.930 121.2 2.7 1.0 2.7 8.4 5.0 0.40 0.520.97 1-10 Example A 0.00202 25.8 266 16.1 9.6 — 126.6 5.7 1.9 3.0 4.64.8 — 0.77 0.29 1-11 Example A 0.00113 11.1 191 0.1 25.7 — 119.2 3.8 3.81.0 13.5 5.8 — 0.48 3.2 1-12 Example A 0.00107 10.4 189 9.5 — — 104.48.7 2.0 4.4 6.6 4.9 — 0.46 0.58 1-13 Compar- E 0.00116 13.2 220 6.4 —0.935 120.5 6.9 2.1 3.3 6.6 3.7 0.30 0.44 0.7 ative Example 1-5 ExampleB 0.00398 29.1 142 12.3 — 0.936 121.9 5.2 1.9 2.7 7.2 4.4 0.40 0.49 0.711-14 Example B 0.00404 25.8 124 9.4 — 0.936 122.1 4.5 2.4 1.9 7.5 4.60.40 0.47 0.96 1-15 Example C 0.00394 29.5 186 8.5 9.4 — 109.5 13.5 10.71.3 8.4 4.5 — 0.41 1.6 1-16

<Evaluation>

As seen from the results shown in Tables 5a-1 and 5a-2, comparingExample 1-1 and Comparative Example 1-1, in Comparative Example 1-1where the polymer was obtained using a catalyst not satisfying therequirements of the metallocene compound of the present invention, theamount of 1-hexene used as a comonomer was large, nevertheless, thedensity of the ethylene-based polymer was not reduced and therefore, itis apparent that the catalyst containing the metallocene compound of thepresent invention as a catalyst component is excellent in the activityas well as in the copolymerizability. Furthermore, in the sameComparative Example 1-1, the amount of hydrogen used as a chain transferagent of polymerization was small, nevertheless, MFR of theethylene-based polymer was not reduced, indicating no increase in themolecular weight, and therefore, it is apparent that the catalystcontaining the metallocene compound of the present invention as acatalyst component has an excellent ability of producing anethylene-based polymer having low MFR (high molecular weight). Moreover,in Example 1-1, all of [λmax(2.0)]_(B), [λmax(2.0)]_(B)/[λmax(0.1)]_(B),g_(C)′ and W_(C), which are characteristic values indicative of theproperty of a long-chain branch of enhancing the moldability of theethylene-based polymer produced, were not inferior to those inComparative Example 1-1 and in addition, the amount of soluble matter at−15° C. (W⁻¹⁵) was small, from which it is apparent that the olefinpolymerization catalyst containing the metallocene compound of thepresent invention as a catalyst component is excellent in themoldability, mechanical properties and the like relative to theethylene-based polymer obtained in Comparative Example 1-1 by usingMetallocene Compound E that is known in Patent Document 4.

The results of Example 1-2 and Comparative Example 1-2 show that thesuperiority of the metallocene compound of the present invention is moreclearly proved by performing an experiment of producing anethylene-based polymer more reduced in the density than in Example 1-1.More specifically, in Comparative Example 1-2 where a catalyst notsatisfying the requirements of the metallocene compound of the presentinvention was used, the influence due to increase of 1-hexene as acomonomer, that is, reduction in activity, increase of g_(C)′ (namely,decrease in the degree of long-chain branching) and increase in theamount of low-temperature soluble fraction, was prominent, whereas inExample 1-2 where the same experiment was performed, a drop of activitywas recognized but the drop width was greatly smaller than inComparative Example 1-2 and at the same time, neither all ofcharacteristic values indicative of long-chain branching weredeteriorated nor increase in the amount of low-temperature elution wasobserved. In other words, it is apparent from Tables 5a-1 and 5a-2 thatthe catalyst containing the metallocene compound of the presentinvention as a catalyst component has a marked superiority in thepolymerization characteristics such as activity, the long-chainbranching characteristics of an ethylene-based polymer, and the amountof a low-temperature eluting component.

Similarly, by comparing the results of Comparative Examples 1-3 and 1-4using Metallocene Compound F or G known in Patent Document 5 with thoseof Examples 1-1 to 1-5, it is apparent that the metallocene compound ofthe present invention is excellent as an olefin polymerization catalystcomponent in terms of overall performance taking into account all of thepolymerization activity, the copolymerizability, the ability to increasethe molecular weight, the long-chain branching characteristics and theamount of a low-temperature eluting component.

Also, Examples 1-6 to 1-8 of Tables 5a-1 and 5a-2 show polymerizationexamples of Metallocene Compound B and Metallocene Compound D, which arethe metallocene compound of the present invention different from that ofExample 1-1. These metallocene compounds of the present invention wereless effective than Metallocene Compound A of Example 1 or the like butexhibited high polymerization activity and furthermore, exhibitedexcellent long-chain branching characteristics represented by largeλmax(2) value, large λmax(2)/λmax(0.1), small g_(C)′ value and largeW_(C) value and in addition, since the W⁻¹⁵ was small and excellentproduct characteristics can be promised, it was confirmed that these aremeaningful metallocene compounds.

In Tables 6a-1 and 6a-2, the catalyst containing the metallocenecompound of the present invention is proved to have usefulness as acatalyst component also in gas-phase polymerization that is apolymerization process different from that of Tables 5a-1 and 5a-2. Morespecifically, comparing Examples 1-9 to 1-13 with Comparative Example1-5, in Comparative Example 1-5 where the polymer was obtained using acatalyst not satisfying the requirements of the metallocene compound ofthe present invention, despite the same amount of 1-butene used as acomonomer, the density of the ethylene-based polymer was increased andtherefore, it is apparent that the catalyst containing the metallocenecompound of the present invention as a catalyst component is excellentin the activity and at the same time, excellent in thecopolymerizability. Furthermore, in the same Comparative Example 1-5,the amount of hydrogen used as a chain transfer agent of polymerizationwas equal, nevertheless, MFR of the ethylene-based polymer was notreduced relative to Example 1-10, indicating no increase in themolecular weight, and therefore, it is apparent that the catalystcontaining the metallocene compound of the present invention as acatalyst component has an excellent ability of producing anethylene-based polymer having low MFR (high molecular weight). Moreover,in Examples 1-9 to 1-13, all of [λmax(2.0)]_(B),[λmax(2.0)]_(B)/[λmax(0.1)]_(B), g_(C)′ and W_(C), which arecharacteristic values indicative of the property of a long-chain branchof enhancing the moldability of the ethylene-based polymer produced,were not inferior to those in Comparative Example 1-5.

Also, Examples 1-14 to 1-16 of Tables 6a-1 and 6a-2 show polymerizationexamples of Metallocene Compound B and Metallocene Compound C, which arethe metallocene compound of the present invention different from thoseof Examples 1-9 to 1-13. These metallocene compounds of the presentinvention exhibited high polymerization activity comparable to that ofMetallocene Compound A of Example 1-10 or the like and furthermore,exhibited any of large λmax(2) value, large λmax(2)/λmax(0.1), smallg_(C)′ value and large W_(C) value and since product characteristicsexcellent in the moldability can be promised, it was confirmed thatthese are meaningful metallocene compounds.

(II) Synthesis of Metallocene Compound

The following metallocene compounds were synthesized and the used as acatalyst component.

[Synthesis Example 1 of Metallocene Compound] (Hereinafter, SometimesSimply Referred to as “Metallocene Compound A”)

Synthesis ofdimethylsilylene(4-tert-butylcyclopentadienyl)(indenyl)zirconiumdichloride was performed according to the procedure described in Example1 of JP-A-09-87314.

[Synthesis Example 2 of Metallocene Compound](Hereinafter, SometimesSimply Referred to as “Metallocene Compound E”)

Synthesis ofdimethylsilylene(3-tert-butylcyclopentadienyl)(cyclopentadienyl)zirconiumdichloride was performed according to the procedure described in J. AM.CHEM. SOC. 2004, 126, 2089-2104.

[Synthesis Example 3 of Metallocene Compound](Hereinafter, SometimesSimply Referred to as “Metallocene Compound F”)

Synthesis of dimethylsilylene(cyclopentadienyl)(indenyl)zirconiumdichloride was performed according to the procedure described inMacromolecules 1995, 28, 3771-3778.

[Synthesis Example 4 of Metallocene Compound](Hereinafter, SometimesSimply Referred to as “Metallocene Compound B”)

Synthesis ofdimethylsilylene(4-tert-butylcyclopentadienyl)(indenyl)hafniumdichloride was performed by the same method as in [Synthesis Example 1]by using hafnium tetrachloride.

[Synthesis Example 5 of Metallocene Compound](Hereinafter, SometimesSimply Referred to as “Metallocene Compound C”)

Synthesis ofdimethylsilylene(3-trimethylsilylcyclopentadienyl)(indenyl)zirconiumdichloride was performed by the same method as in [Synthesis Example 1]by using (3-trimethylsilylcyclopentadienyl)(indenyl)dimethylsilane.

[Synthesis Example 6 of Metallocene Compound](Hereinafter, SometimesSimply Referred to as “Metallocene Compound D”)

Synthesis ofisopropylidene(4-tert-butylcyclopentadienyl)(indenyl)zirconiumdichloride was performed by the same method as in [Synthesis Example 1]by using (4-tert-butylcyclopentadienyl)(indenyl)dimethylmethane, and thetarget metallocene was obtained as an isomeric mixture.

Example 2-1 (1) Preparation of Solid Catalyst

In a nitrogen atmosphere, 5 g of silica calcined at 600° C. for 5 hourswas put in a 200-ml two-neck flask and dried at reduced pressure with avacumn pump for 1 hour while heating the flask in an oil bath at 150° C.In a nitrogen atmosphere, 57 mg of Metallocene Compound A was put in aseparately prepared 100-ml two-neck flask and dissolved in 13.4 ml ofdehydrated toluene, and to the resulting toluene solution of MetalloceneCompound A, 8.6 ml of a 20% methylaluminoxane/toluene solution producedby Albemarle was added at room temperature and stirred for 30 minutes.While heating the 200-ml two-neck flask containing vacuum-dried silicain an oil bath at 40° C. and stirring the contents, the entire amount ofthe toluene solution above containing a reaction product of MetalloceneCompound A and methylaluminoxane was added and stirred at 40° C. for 1hour. While still heating the system at 40° C. the toluene solvent wasremoved by distillation under reduced pressure to obtain a solidcatalyst.

(2) Production of Ethylene.1-Butene Copolymer

An ethylene.1-butene copolymer was produced using the solid catalystobtained in (1) Preparation of Solid Catalyst above.

That is, 80 g of polyethylene-made pellets subjected to fill dehydrationand deoxidation and 33 mg of triethylaluminum were introduced into astainless steel-made autoclave having an internal volume of 1 liter andhaving stirring and temperature control devices, and the temperature wasraised to 90° C. under stirring. After introducing ethylene containing10 wt % of 1-butene until the partial pressure became 2.0 MPa, 50 mg ofthe solid catalyst obtained above was injected with an argon gas, andpolymerization was performed for 60 minutes.

As a result, 20.3 g of an ethylene.1-butene copolymer was produced. Thepolymerization results are shown in Tables 7a-1 and 7a-2.

Comparative Example 2-1 (1) Preparation of Solid Catalyst

A solid catalyst was prepared in the same manner as in Example 2-1except for using 51 mg of Metallocene Compound E obtained in SynthesisExample 2 in place of 57 mg of Metallocene Compound A.

(2) Production of Ethylene.1-Butene Copolymer

An ethylene.1-butene copolymer was produced in the same manner as inExample 2-1 except that 56 mg of the solid catalyst obtained inPreparation of Solid Catalyst above was used in place of 50 mg of thesolid catalyst obtained in Example 2-1 and the polymerization wasperformed at a polymerization temperature of 80° C. for 51 minutes.

As a result, 25.8 g of an ethylene.1-butene copolymer was produced. Thepolymerization results are shown in Tables 7a-1 and 7a-2.

Example 2-2 (2) Production of Ethylene.1-Hexene Copolymer

An ethylene.1-hexene copolymer was produced using the solid catalystobtained in Example 2-1.

That is, 50 g of polyethylene-made pellets subjected to full dehydrationand deoxidation and 0.20 mmol of triethylaluminum were introduced into astainless steel-made autoclave having an internal volume of 2 liter andhaving stirring and temperature control devices, and the temperature wasraised to 75° C. under stirring. After introducing 1.5 ml of 1-hexeneand ethylene until the partial pressure became 1.4 MPa, 64 mg of thesolid catalyst obtained above was injected with a nitrogen gas, andpolymerization was performed for 90 minutes. Incidentally, during thepolymerization reaction, additional feeding of 1-hexene was performed ata feed rate proportional to the ethylene consumption rate. As a result,the molar ratio of H₂/C₂ (hydrogen/ethylene) in the autoclave gas phasepart at 10 minutes after the initiation of polymerization and just priorto stopping of the polymerization was 0.093% and 0.104%, respectively,and the amount of 1-hexene additionally fed was 9.5 mL. As a result,49.5 g of an ethylene 1-hexene copolymer was produced. Thepolymerization results are shown in Tables 7a-1 and 7a-2.

Comparative Example 2-2

An ethylene.1-hexene copolymer was produced in the same manner as inExample 2-2 except that 62 mg of the solid catalyst obtained inPreparation of Solid Catalyst of Comparative Example 2-1 was used inplace of 64 mg of the solid catalyst obtained in Example 2-1. However,the amount of 1-hexene additionally fed was 7.5 mL. The molar ratio ofH₂/C₂ (hydrogen/ethylene) in the autoclave gas phase part at 10 minutesafter the initiation of polymerization and just prior to stopping of thepolymerization was 0.122% and 0.137%, respectively. As a result, 42.0 gof an ethylene.1-hexene copolymer was produced. The polymerizationresults are shown in Tables 7a-1 and 7a-2.

Comparative Example 2-3 (1) Preparation of Solid Catalyst

A solid catalyst was prepared in the same manner as in Example 2-1except for using 50 mg of Metallocene Compound F obtained in SynthesisExample 3 in place of 57 mg of Metallocene Compound A.

(2) Production of Ethylene.1-Hexene Copolymer

An ethylene.1-hexene copolymer was produced in the same manner as inExample 2-1 except that 194 mg of the solid catalyst obtained in (1)Preparation of Solid Catalyst above was used, ethylene containing 10 wt% of 1-hexene was used in place of ethylene containing 10 wt % of1-butene, and the polymerization temperature was set to 70° C.

As a result, 13.7 g of an ethylene.1-hexene copolymer was produced. Thepolymerization results are shown in Tables 7a-1 and 7a-2.

Reference Example 2-1 (2) Production of Ethylene.1-Hexene Copolymer

An ethylene.1-hexene copolymer was produced in the same manner as inExample 2-1 except that 52 mg of the solid catalyst obtained in Example2-1 was used and ethylene containing 10 wt % of 1-hexene was used inplace of ethylene containing 10 wt %° of 1-butene.

As a result, 17.5 g of an ethylene.1-hexene copolymer was produced. Thepolymerization results are shown in Tables 7a-1 and 7a-2.

Comparative Example 2-4 (1) Preparation of Solid Catalyst

A solid catalyst was prepared in the same manner as in Example 2-1except for using 44 mg of Metallocene Compound G produced by Wako PureChemical Industries, Ltd. in place of 57 mg of Metallocene Compound A.

(2) Production of Ethylene.1-Hexene Copolymer

An ethylene.1-hexene copolymer was produced in the same manner as inExample 2-1 except that 49 mg of the solid catalyst obtained inPreparation of Solid Catalyst above was used and ethylene containing 5wt % of 1-hexene was used in place of ethylene containing 10 wt % of1-butene.

As a result, 4.5 g of an ethylene.1-hexene copolymer was produced. Thepolymerization results are shown in Tables 7a-1 and 7a-2.

Comparative Example 2-5 (1) Production of Ethylene Polymer

An ethylene polymer was produced using the solid catalyst obtained inPreparation of Solid Catalyst of Comparative Example 2-4.

That is, 800 mL of isobutane and 0.20 mmol of triethylaluminum wereadded to a 2 L-volume autoclave with an induction stirring device, thetemperature was raised to 75° C., and the ethylene partial pressure waskept at 1.4 MPa by introducing ethylene. Subsequently, 525 mg of thesolid catalyst of Comparative Example 2-4 was injected with nitrogen andafter continuing the polymerization for 60 minutes by keeping theethylene partial pressure of 1.4 MPa and the temperature of 75° C., thepolymerization was stopped by adding ethanol. The molar ratio of H₂/C₂(hydrogen/ethylene) in the autoclave gas phase part just prior tostopping of the polymerization was 0.088%. The amount of thethus-obtained ethylene polymer was 60.0 g. The polymerization resultsare shown in Tables 7a-1 and 7a-2.

Example 2-3 (2) Production of Ethylene.1-Butene Copolymer

An ethylene.1-butene copolymer was produced in the same manner as inExample 2-1 except that 55 mg of the solid catalyst obtained in Example2-1 was used and the polymerization was performed at a polymerizationtemperature of 70° C. for 31 minutes.

As a result, 25.6 g of an ethylene.1-butene copolymer was produced. Thepolymerization results are shown in Tables 7a-1 and 7a-2.

Reference Example 2-2 (1) Preparation of Triethylaluminum-TreatedMontmorillonite

In a nitrogen atmosphere, 3.0 g of commercially availablemontmorillonite was put in a 200-ml two-neck flask and dried at reducedpressure with a vacuum pump for 1 hour while heating the flask in an oilbath at 200° C. After cooling to room temperature. 75 ml of heptane wasadded to make a slurry, and 14.4 ml of triethylaluminum (a heptanesolution at a concentration of 70 g/liter) was added with stirring.After stirring at room temperature for 1 hour, the solid was washed bydecantation to a dilution ratio of 1/100. Finally, heptane was addeduntil reaching a liquid volume of 150 ml to obtain a slurry oftriethylahuninum-treated montmorillonite.

(2) Production of Ethylene.1-Hexene Copolymer

An ethylene.1-hexene copolymer was produced using thetriethylaluminum-treated montmorillonite of (l) above.

That is, 500 ml of heptane subjected to full dehydration, 55 mg oftriethylaluminum and 10 ml of 1-hexene were introduced into a stainlesssteel-made autoclave having an internal volume of I liter and havingstirring and temperature control devices, and the temperature was raisedto 80° C. under stirring. After introducing ethylene until the partialpressure became 1.5 MPa, 50 mg of the triethylaluninum-treatedmountmorillonite (2.5 ml of a heptane slurry) and 2.5 micromol ofMetallocene Compound A were injected with an argon gas, andpolymerization was performed for 60 minutes. During the polymerizationreaction, the pressure was kept at 1.5 MPa by introducing ethylenecontaining 10 wt % of 1-hexene according to the ethylene consumption inthe system.

As a result, 3.0 g of an ethylene.1-hexene copolymer was produced. Thepolymerization results are shown in Tables 7a-1 and 7a-2.

Example 2-4 (1) Preparation of Solid Catalyst

A solid catalyst was prepared in the same manner as in Example 2-1except for using 68 mg of Metallocene Compound B obtained in SynthesisExample 2-4 in place of 57 mg of Metallocene Compound A.

(2) Production of Ethylene.1-Butene Copolymer

An ethylene.1-butene copolymer was produced in the same manner as inExample 2-1 except that 210 mg of the solid catalyst obtained inPreparation of Solid Catalyst above was used in place of 50 mg of thesolid catalyst obtained in Example 2-1 and 34 ml of hydrogen was added.

As a result, 10.0 g of an ethylene.1-butene copolymer was produced. Thepolymerization results are shown in Tables 7a-1 and 7a-2.

Example 2-5 (1) Preparation of Solid Catalyst

A solid catalyst was prepared in the same manner as in Example 2-1except for using 59 mg of Metallocene Compound C obtained in SynthesisExample 5 in place of 57 mg of Metallocene Compound A.

(2) Production of Ethylene.1-Butene Copolymer

An ethylene.1-butene copolymer was produced in the same manner as inExample 2-1 except that 54 mg of the solid catalyst obtained inPreparation of Solid Catalyst above was used in place of 50 mg of thesolid catalyst obtained in Example 2-1.

As a result, 16.5 g of an ethylene.1-butene copolymer was produced. Thepolymerization results are shown in Tables 7a-1 and 7a-2.

Example 2-6 (1) Preparation of Solid Catalyst

A solid catalyst was prepared in the same manner as in Example 2-1except for using 55 mg of Metallocene Compound D obtained in SynthesisExample 6 in place of 57 mg of Metallocene Compound A.

(2) Production of Ethylene.1-Hexene Copolymer

An ethylene.1-hexene copolymer was produced using the solid catalystobtained in (1) Preparation of Solid Catalyst above.

That is, 800 mL of isobutane, 40 mL of 1-hexene and 0.20 mmol oftriethylaluminum were added to a 2 L-volume autoclave with an inductionstirring device, the temperature was raised to 75° C., and the ethylenepartial pressure was kept at 1.4 MPa by introducing ethylene.

Subsequently, 180 mg of the solid catalyst obtained in (1) above wasinjected with nitrogen and after continuing the polymerization for 60minutes by keeping the ethylene partial pressure of 1.4 MPa and thetemperature of 75° C., the polymerization was stopped by adding ethanol.Incidentally, during the polymerization reaction, additional feeding of1-hexene was performed at a feed rate proportional to the ethyleneconsumption rate. As a result, the average molar ratio of H₂/C₂(hydrogen/ethylene) in the autoclave gas phase part at 10 minutes afterthe initiation of polymerization and just prior to stopping of thepolymerization was 0.098%0, and the amount of 1-hexene fed additionallywas 12 mL. The amount of the thus-obtained ethylene-based polymer was48.5 g. The polymerization results are shown in Tables 7a-1 and 7a-2.

TABLE 63 [Table 7a-1] Catalyst Component (A) Component (B) Component (C)Amount Metal- Amount Amount Amount of Solid locene Used Used UsedCatalyst Compound (mmol) Compound (mmol) Compound (g) (g) Example 2-1 A0.00097 MAO 0.19 silica 0.039 0.050 Comparative E 0.00109 MAO 0.22silica 0.044 0.056 Example 2-1 Example 2-2 A 0.00123 MAO 0.25 silica0.049 0.064 Comparative E 0.00120 MAO 0.24 silica 0.048 0.062 Example2-2 Comparative F 0.00376 MAO 0.75 silica 0.150 0.194 Example 2-3Reference A 0.00099 MAO 0.20 silica 0.040 0.052 Example 2-1 ComparativeG 0.00142 MAO 0.28 silica 0.057 0.049 Example 2-4 Comparative G 0.01010MAO 2.02 silica 0.404 0.525 Example 2-5 Example 2-3 A 0.00107 MAO 0.21silica 0.043 0.055 Reference A 0.00250 montmo- 0.050 g — — 0.050 Example2-2 rillonite Example 2-4 B 0.00407 MAO 0.81 silica 0.163 0.210 Example2-5 C 0.00105 MAO 0.21 silica 0.042 0.054 Example 2-6 D 0.00346 MAO 0.69silica 0.138 0.180 Polymerization Conditions Comonomer C2 Polymer-Hydrogen Initial Additional Temper- Partial ization TEA H2/C2 ChargeAmount ature Pressure Time (mmol) Solvent (%) (ml) (ml) (° C.) (MPa)(min) Example 2-1 0.30 gas 0.030 C4/C2 = 5.0 mol % 90 2.0 60 phaseComparative 0.30 gas 0.028 C4/C2 = 5.0 mol % 80 2.0 51 Example 2-1 phaseExample 2-2 0.20 gas 0.098 1.5 ml 9.5 ml 75 1.4 90 phase Comparative0.20 gas 0.129 1.5 ml 7.5 ml 75 1.4 90 Example 2-2 phase Comparative0.30 gas 0.022 C6/C2 = 3.3 mol % 70 2.0 60 Example 2-3 phase Reference0.30 gas 0.009 C6/C2 = 3.3 mol % 90 2.0 60 Example 2-1 phase Comparative0.30 gas 0.015 C6/C2 = 1.7 mol % 90 2.0 105 Example 2-4 phaseComparative 0.20 iso- 0.088 — — 75 1.4 60 Example 2-5 butane Example 2-30.30 gas 0.026 C4/C2 = 5.0 mol % 70 2.0 31 phase Reference 0.50 heptane0.004  10 ml C6/C2 = 80 1.5 60 Example 2-2 3.3 mol % Example 2-4 0.30gas 0.080 C4/C2 = 5.0 mol % 90 2.0 60 phase Example 2-5 0.30 gas 0.030C4/C2 = 5.0 mol % 90 2.0 60 phase Example 2-6 0.20 iso- 0.098  40 ml  12ml 75 1.4 60 butane Metallocene Compound A

B

C (isomeric mixture)

D (isomeric mixture)

E

F

G

TABLE 7a-2 Catalyst Results Component (A) Activ- Terminal Metal- ityDen- λmax Double locene Amount (g-PE/ MFR sity (2.0)/ Bond Com- UsedYield g-Cat/ (g/10 (g/ λmax λmax λmax Mw Mw/ (bonds/ g_(c)′ W_(c) Valuepound (mmol) (g) hr) min) FR cm3) (2.0) (0.1) (0.1) ×10⁴ Mn 1000 C.)Value (MW ≧10{circumflex over ( )}6) Example A 0.00097 20.3 406 16.6 —0.938 7.0 4.9 1.4 6.1 3.8 0.30 0.44 1.0 2-1 Compar- E 0.00109 25.8 54211.3 — 0.940 4.2 3.4 1.2 5.9 2.7 0.63 0.62 0.1 ative Example 2-1 ExampleA 0.00123 49.5 516 38.3 — 0.927 — — — 4.4 3.3 — 0.36 0.8 2-2 Compar- E0.00120 42.0 451 23.9 8.0 0.930 4.7 3.1 1.5 4.9 3.2 — 0.38  0.09 ativeExample 2-2 Compar- F 0.00376 13.7 70 15.1 6.1 0.931 36.7 19.6 1.9 5.53.8 0.35 0.79 0.7 ative Example 2-3 Reference A 0.00099 17.5 337 0.05(HL) — 0.912 — — — 58.4 3.4 0.00 — — Example 2-1 Compar- G 0.00142 4.552 22.7 — 0.958 10.9 18.9 0.6 5.3 4.1 1.31 0.90 0.9 ative Example 2-4Compar- G 0.01010 60.0 114 11.5 9.5 0.960 7.0 7.0 1.0 5.7 3.9 — — —ative Example 2-5 Example A 0.00107 25.6 902 1.3 13.0  0.930 2.8 1.5 1.97.5 3.7 — — — 2-3 Reference A 0.00250 3.0 60 0.02 (HL) — 0.920 — — —106.0 2.9 0.23 — — Example 2-2 Example B 0.00407 10.0 48 7.8 7.9 0.945 —— — 6.8 4.1 — 1.00 0.5 2-4 Example C 0.00105 16.5 306 9.7 6.9 0.942 3.01.8 1.7 7.2 4.0 — 1.00 0.2 2-5 Example D 0.00346 48.5 270 116 — 0.935 —— — 2.8 3.3 — 0.74 0.2 2-6

As seen from the results shown in Tables 7a-1 and 7a-2, comparingExample 2-1 and Comparative Example 2-1 or comparing Example 2-2 andComparative Example 2-2, in the ethylene-based polymers of ComparativeExamples 2-1 and 2-2 obtained using a catalyst not satisfying therequirements of the metallocene compound of the present invention, the[λmax(2.0)]_(B) of the requirement (B-4′-i) or[λmax(2.0)]_(B)/[λmax(0.1)]_(B) of the requirement (B-4′-ii) wasinferior, g_(C)′ of the requirement (B-4′-iii) was not sufficientlyreduced, or W_(C) of the requirement (B-4′-iv) was poor. From these, itis apparent that the ethylene-based polymer produced in Examplesaccording to the present invention is excellent in the moldability.

Also, as compared with the polymerization activity in Examples 2-1 and2-2 of Tables 7a-1 and 7a-2, the polymerization activity in ethylenepolymerization by a catalyst not satisfying the requirements of themetallocene compound of the present invention was significantly low asseen in Comparative Examples 2-3 to 2-5, and evidently, there is aproblem in profitability as the production method of an ethylene-basedpolymer. Furthermore, [λmax(2.0)]_(B) of the ethylene-based polymerobtained in Comparative Example 2-3 was too large, and this clearlyindicates that only an ethylene-based polymer with poor strength can beobtained. In addition, the ethylene-based polymer obtained inComparative Example 2-4 or 2-5 was poor in the[λmax(2.0)]_(B)/[λmax(0.1)]_(B) of the requirement (B-4′-ii). Fromthese, it is apparent that the ethylene-based polymer produced inExamples according to the present invention is excellent in themoldability and excellent also in the profitability.

Examples 2-4 to 2-6 of Tables 7a-1 and 7a-2 are a case using ametallocene compound differing in the structure from the catalystsatisfying the requirements of the metallocene compound of the presentinvention used in Examples 2-1 to 2-3.

In the case of the metallocene compound of Example 2-4 which differsfrom the metallocene compound of Example 2-1 only in that the centermetal species is Hf or Zr, while having the same ligand structure, theactivity was inferior to that in Example 2-1, but W_(C) of therequirement (B-4′-iv) of the present invention showed a relatively largevalue, and it is estimated that the ethylene-based polymer hasadequately excellent moldability.

In the case of the metallocene compound of Example 2-5 which differsfrom the metallocene compound of Example 2-1 only in that thesubstituent on the cyclopentadienyl ring is a trimethylsilyl group or atert-butyl group, while having the same structure in the rest, highactivity equal to that in Example 2-1 was exhibited and the requirements(B-4′-i), (B-4′-ii) and (B-4′-iv) of the present invention were fullysatisfied, indicating that the ethylene-based polymer is excellent inthe moldability.

In the case of the metallocene compound of Example 2-6 which differsfrom the metallocene compound of Example 2-1 only in that the bridginggroup connecting the cyclopentadienyl ring and the indenyl ring is ani-propyl group or a dimethylsilylene group, while having the samestructure in the rest, high activity equal to that in Example 2-1 wasexhibited and the requirements (B-4′-iv) was satisfied, indicating thatthe ethylene-based polymer is excellent in the moldability.

From these, it is verified that all of ethylene-based polymers producedwith catalysts using metallocene compounds belonging to the presentinvention can express sufficiently improved moldability.

While the invention has been described in detail and with reference tospecific embodiments thereof, it will be apparent to one skilled in theart that various changes and modifications can be made therein withoutdeparting from the spirit and scope of the invention. This applicationis based on Japanese Patent Application (Patent Application No.2011-073937) filed on Mar. 30, 2011, and Japanese Patent Application(Patent Application No. 2011-073945) filed on Mar. 30, 2011, thecontents of which are incorporated herein by way of reference.

INDUSTRIAL APPLICABILITY

As clearly understood from the description in the foregoing pages, thepolyethylene-based resin composition of the present invention hasexcellent molding characteristics and at the same time, has an effectthat the balance between impact strength and stiffness is excellent andfurthermore, the transparency is excellent. In addition, the moldedproduct obtained by the injection molding, compression-injectionmolding, rotational molding, extrusion molding, hollow molding or blowmolding of the polyethylene-based resin composition is also excellent inthe balance between impact strength and stiffness as well as in thetransparency, so that a molded product reduced in the wall thickness canbe provided in an economically advantageous manner.

Accordingly, the polyethylene-based resin composition of the presentinvention capable of providing a molded product having such desiredproperties in an economically advantageous manner has a significantlyhigh industrial value.

Moreover, an olefin polymerization catalyst capable of introducing asufficiently large number of appropriate length long-chain branches intoan olefin polymer is obtained by using the olefin polymerizationcatalyst component of the present invention, and an olefin-based polymerusefiul, for example, in substituting for a high-pressure low-densitypolyethylene excellent in moldability, substituting for a high-densitypolyethylene obtained with a chromium-based catalyst, or improving themoldability of a metallocene polymer is obtained. For these reasons, theolefin polymerization catalyst of the present invention is of highsignificance and has very great industrial applicability.

1-14. (canceled)
 15. An olefin polymerization catalyst component,comprising the following component (A-1b) and component (A-2b):component (A-1 b): a metallocene compound represented by the followingformula (3b):

in formula (3b), M^(1b) represents any one transition metal of Ti, Zrand Hf; each of X^(1b) and X^(2b) independently represents a hydrogenatom, a halogen atom, a hydrocarbon group having a carbon number of 1 to20, a hydrocarbon group containing an oxygen atom or a nitrogen atom andhaving a carbon number of 1 to 20, a hydrocarbon group-substituted aminogroup having a carbon number of 1 to 20, or an alkoxy group having acarbon number of 1 to 20; each of Q^(1b) and Q^(2b) independentlyrepresents a carbon atom, a silicon atom or a germanium atom; eachR^(1b) independently represents a hydrogen atom or a hydrocarbon grouphaving a carbon number of 1 to 10 and at least two members out of fourR^(1b) may combine to form a ring together with Q^(1b) and Q^(2b); m^(b)is 0 or 1 and when m^(b) is 0, Q^(1b) is bonded directly to theconjugated 5-membered ring including R^(2b) and R^(3b); and each ofR^(2b), R^(3b) and R^(4b) independently represents a hydrogen atom, ahalogen atom, a hydrocarbon group having a carbon number of 1 to 20, asilicon-containing hydrocarbon group containing from 1 to 6 silicons andhaving a carbon number of 1 to 18, a halogen-containing hydrocarbongroup having a carbon number of 1 to 20, a hydrocarbon group containingan oxygen atom or a sulfur atom and having a carbon number of 1 to 40,or a silyl group substituted with a hydrocarbon group having a carbonnumber of 1 to 40 and out of R^(2b), R^(3b) and R^(4b), only either onepair of adjacent R^(3b) and R^(3b) and adjacent R^(2b) and R^(3b) mayform a ring together with the carbon atoms to which the pair is bonded,and component (A-2b): a metallocene compound represented by thefollowing formula (8b) or (9b):

in formula (8b), M^(2b) represents any one transition metal of Ti, Zrand Hf; each of X^(11b) and X^(12b) independently represents a hydrogenatom, a halogen atom, a hydrocarbon group having a carbon number of 1 to20, a hydrocarbon group containing an oxygen atom or a nitrogen atom andhaving a carbon number of 1 to 20, a hydrocarbon group-substituted aminogroup having a carbon number of 1 to 20, or an alkoxy group having acarbon number of 1 to 20; Q^(11b) represents a carbon atom, a siliconatom or a germanium atom; each R^(11b) independently represents ahydrogen atom or a hydrocarbon group having a carbon number of 1 to 10and two R^(11b) may combine with each other to form a ring together withQ^(11b); each of R^(12b), R^(14b), R^(18b) and R^(19b) independentlyrepresents a hydrogen atom, a halogen atom, a hydrocarbon group having acarbon number of 1 to 20, a silicon-containing hydrocarbon groupcontaining from 1 to 6 silicons and having a carbon number of 1 to 18, ahalogen-containing hydrocarbon group having a carbon number of 1 to 20,a hydrocarbon group containing an oxygen atom or a sulfur atom andhaving a carbon number of 1 to 40, or a silyl group substituted with ahydrocarbon group having a carbon number of 1 to 40, provided thatR^(12b) and R^(14b) do not form a ring together with the carbon atoms towhich these members are bonded; R^(18b) and R^(19b) may form a ringtogether with the carbon atoms to which these members are bonded; andR^(12b) on the 2-position include an oxygen-containing heterocyclicgroup and a sulfur-containing heterocyclic group, represented by thefollowing formula (10b):

in formula (10b), R^(21b) and R^(22b) may be the same as or differentfrom each other and is a hydrogen atom, a halogen atom, an alkyl grouphaving a carbon number of 1 to 6, an alkoxy group having a carbon numberof 1 to 6, an alkenyl group having a carbon number of 2 to 8, ahalogen-containing alkyl group having a carbon number of 1 to 6, an arylgroup having a carbon number of 6 to 18, a halogen-containing aryl grouphaving a carbon number of 6 to 18, an alkyl group having a carbon numberof 1 to 3 and containing a trialkylsilyl group with the alkyl grouphaving a carbon number of 1 to 3, or a silyl group containing ahydrocarbon group having a carbon number of 1 to
 6. Both of R^(21b) andR^(22b) may together constitute a 6- or 7-membered ring, and the 6- or7-membered ring may contain an unsaturated bond;

in formula (9b), M^(2b) represents any one transition metal of Ti, Zrand Hf; each of X^(11b) and X^(12b) independently represents a hydrogenatom, a halogen atom, a hydrocarbon group having a carbon number of 1 to20, a hydrocarbon group containing an oxygen atom or a nitrogen atom andhaving a carbon number of 1 to 20, a hydrocarbon group-substituted aminogroup having a carbon number of 1 to 20, or an alkoxy group having acarbon number of 1 to 20; Q^(11b) represents a carbon atom, a siliconatom or a germanium atom; each R^(11b) independently represents ahydrogen atom or a hydrocarbon group having a carbon number of 1 to 10and two R^(11b) may combine with each other to form a ring together withQ^(11b); each of R^(12b), R^(14b) and R^(15b) independently represents ahydrogen atom, a halogen atom, a hydrocarbon group having a carbonnumber of 1 to 20, a silicon-containing hydrocarbon group containingfrom 1 to 6 silicons and having a carbon number of 1 to 18, ahalogen-containing hydrocarbon group having a carbon number of 1 to 20,a hydrocarbon group containing an oxygen atom or a sulfur atom andhaving a carbon number of 1 to 40, or a silyl group substituted with ahydrocarbon group having a carbon number of 1 to 40, provided that atleast one of R^(12b) located on the 2-position of the indenyl ring andR^(14b) and R^(15b) located on the 2-position and 5-position of thecyclopentadienyl ring is not a hydrogen atom and R^(12b), R^(14b) andR^(15b) do not form a ring together with the carbon atoms to which thesemembers are bonded; and R^(18b) may form a ring together with the carbonatom to which R^(18b) is bonded.
 16. An olefin polymerization catalystcomponent, comprising a metallocene compound represented by thefollowing formula (1c):

in formula (1c), M^(1c) represents any one transition metal of Ti, Zrand Hf; each of X^(1c) and X^(2c) independently represents a hydrogenatom, a halogen atom, a hydrocarbon group having a carbon number of 1 to20, a hydrocarbon group containing an oxygen atom or a nitrogen atom andhaving a carbon number of 1 to 20, a hydrocarbon group-substituted aminogroup having a carbon number of 1 to 20, or an alkoxy group having acarbon number of 1 to 20; each of Q^(1c) and Q^(2c) independentlyrepresents a carbon atom, a silicon atom or a germanium atom; eachR^(1c) independently represents a hydrogen atom or a hydrocarbon grouphaving a carbon number of 1 to 10 and at least two members out of fourR^(1c) may combine to form a ring together with Q^(1c) and Q^(2c); m^(c)is 0 or 1 and when m^(c) is 0, Q^(1c) is bonded directly to theconjugated 5-membered ring including R^(2c); each of R^(2c) and R^(4c)independently represents a hydrogen atom, a halogen atom, a hydrocarbongroup having a carbon number of 1 to 20, a silicon-containinghydrocarbon group containing from 1 to 6 silicons and having a carbonnumber of 1 to 18, a halogen-containing hydrocarbon group having acarbon number of 1 to 20, a hydrocarbon group containing an oxygen atomand having a carbon number of 1 to 20, or a hydrocarbongroup-substituted silyl group having a carbon number of 1 to 20; andR^(3c) represents a substituted aryl group represented by the followingformula (1-ac):

in formula (1-ac), Y^(1c) represents an atom of Group 14, Group 15 orGroup 16 of the periodic table; each of R^(5c), R^(6c), R^(7c), R^(8c)and R^(9c) independently represents a hydrogen atom, a fluorine atom, achlorine atom, a bromine atom, a hydrocarbon group having a carbonnumber of 1 to 20, a hydrocarbon group containing oxygen or nitrogen andhaving a carbon number of 1 to 20, a hydrocarbon group-substituted aminogroup having a carbon number of 1 to 20, an alkoxy group having a carbonnumber of 1 to 20, a silicon-containing hydrocarbon group containingfrom 1 to 6 silicons and having a carbon number of 1 to 18, ahalogen-containing hydrocarbon group having a carbon number of 1 to 20,or a hydrocarbon group-substituted silyl group having a carbon number of1 to 20; adjacent groups of R^(5c), R^(6c), R^(7c), R^(8c) and R^(9c)may combine with each other to form a ring together with the atomsbonded to these groups; n^(c) is 0 or 1 and when n^(c) is 0, thesubstituent R^(5c) is not present on Y^(1c); and p^(c) is 0 or 1 andwhen p^(c) is 0, the carbon atom to which R^(7c) is bonded and thecarbon atom to which R^(9c) is bonded are bonded directly; provided thatwhen Y^(1c) is a carbon atom, at least one of R^(5c), R^(6c), R^(7c),R^(8c) and R^(9c) is not a hydrogen atom.
 17. An olefin polymerizationcatalyst, comprising the olefin polymerization catalyst componentclaimed in claim
 15. 18. A production method of an ethylene-basedpolymer, comprising polymerizing a monomer in the presence of an olefinpolymerization catalyst comprising the following components (A) and (B):component (A): at least any one of the following catalyst components(A-i) to (A-iii): (A-i) the olefin polymerization catalyst componentclaimed claim 15, (A-ii) the olefin polymerization catalyst componentclaimed in claim 10, and (A-iii) an olefin polymerization catalystcomponent containing a metallocene compound represented by the followingformula (1d):

in formula (1 d), M^(1d) represents any one transition metal of Ti, Zrand Hf; each of XId and X^(2d) independently represents a hydrogen atom,a halogen atom, a hydrocarbon group having a carbon number of 1 to 20, ahydrocarbon group containing an oxygen atom or a nitrogen atom andhaving a carbon number of 1 to 20, a hydrocarbon group-substituted aminogroup having a carbon number of 1 to 20, or an alkoxy group having acarbon number of 1 to 20; each of Q^(1d) and Q^(2d) independentlyrepresents a carbon atom, a silicon atom or a germanium atom; eachR^(1d) independently represents a hydrogen atom or a hydrocarbon grouphaving a carbon number of 1 to 10 and at least two members out of fourR^(1d) may combine to form a ring together with Q^(1d) and Q^(2d); m^(d)is 0 or 1 and when m^(d) is 0, Q^(1d) is bonded directly to theconjugated 5-membered ring including R^(2d) and R^(3d); each of R^(2d)and R^(3d) represents a hydrogen atom, a halogen atom, a hydrocarbongroup having a carbon number of 1 to 20, a silicon-containinghydrocarbon group containing from 1 to 6 silicons and having a carbonnumber of 1 to 18, a halogen-containing hydrocarbon group having acarbon number of 1 to 20, a hydrocarbon group containing an oxygen atomand having a carbon number of 1 to 20, or a hydrocarbongroup-substituted silyl group having a carbon number of 1 to 20,provided that at least one R^(2d) is not a hydrogen atom; R^(4d)represents a saturated or unsaturated divalent hydrocarbon group havinga carbon number of 4 or 5 for forming a condensed ring with the5-membered ring to which R^(4d) is bonded; R^(5d) is an atom or a groupbonded to a carbon atom of R^(4d) and each independently represents ahydrogen atom, a halogen atom, a hydrocarbon group having a carbonnumber of 1 to 20, a silicon-containing hydrocarbon group containingfrom 1 to 6 silicons and having a carbon number of 1 to 18, ahalogen-containing hydrocarbon group having a carbon number of 1 to 20,a hydrocarbon group containing an oxygen atom and having a carbon numberof 1 to 20, or a hydrocarbon group-substituted silyl group having acarbon number of 1 to 20; and n^(d) represents an integer of 0 to 10 andwhen n^(d) is 2 or more, at least two R^(5d) may form a ring togetherwith the carbon atoms to which R^(5d) are bonded, and component (B): acompound capable of reacting with a metallocene compound of thecomponent (A) to produce a cationic metallocene compound.
 19. Anethylene-based polymer which is produced by the method of claim 18.